Pesticidal compositions and related methods

ABSTRACT

A pesticidal composition comprises a compound of formula I or any agriculturally acceptable salt thereof, wherein R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , Z, Q, and Y are as described herein. A method of controlling pests comprises applying the pesticidal composition near a population of pests, or to an area to control pests.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/894,281, filed Oct. 22, 2013, the disclosure ofwhich is hereby incorporated herein in its entirety by this reference.

TECHNICAL FIELD

This disclosure relates to the field of compounds having pesticidalutility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca,processes to produce such compounds and intermediates used in suchprocesses. These compounds may be used, for example, as nematicides,acaricides, insecticides, miticides, and/or molluscicides.

BACKGROUND

Controlling pest populations is essential to human health, modernagriculture, food storage, and hygiene. There are more than ten thousandspecies of pests that cause losses in agriculture and the world-wideagricultural losses amount to billions of U.S. dollars each year.Accordingly, there exists a continuous need for new pesticides and formethods of producing and using such pesticides.

DETAILED DESCRIPTION Definitions

The examples given in the definitions are non-exhaustive and must not beconstrued as limiting the present disclosure. It is understood that asubstituent should comply with chemical bonding rules and stericcompatibility constraints in relation to the particular molecule towhich it is attached.

“Alkyl” means and includes an acyclic, saturated, branched or unbranchedhydrocarbon. Non-limiting examples may include methyl, ethyl, propyl,isopropyl, -butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl,1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, or decyl,

“Cycloalkyl” means and includes a monocyclic or polycyclic saturatedhydrocarbon. Non-limiting examples may include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl,bicyclo[2.2.2]octyl, or decahydronapthyl.

“Alkenyl” means and includes an acyclic, branched or unbranchedhydrocarbon containing at least one carbon-carbon double bond.Non-limiting examples may include ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, or decenyl.

“Cycloalkenyl” means and includes a monocyclic or polycyclic hydrocarboncontaining at least one carbon-carbon double bond. Non-limiting examplesmay include cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, orcyclodecenyl.

“Alkynyl” means and includes acyclic, branched or unbranched hydrocarboncontaining at least one carbon-carbon triple bond. Non-limiting examplesmay include ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl,octynyl, nonynyl, or decynyl.

“Cycloalkynyl” means and includes a monocyclic or polycyclic hydrocarboncontaining at least one carbon-carbon triple bond. Non-limiting examplesmay include cycloheptynyl, cyclooctynyl, or cyclodecynyl.

“Aryl” means and includes an aromatic compound with or without anysubstitution. Non-limiting examples may include phenyl or naphthyl.

“Alkoxy” means and includes an alkyl group containing at least onecarbon-oxygen single bond. Non-limiting examples may include methoxy,ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, or cyclopentoxy.

“Alkenyloxy” means and includes an alkenyl containing at least onecarbon-oxygen single bond. Non-limiting examples may include allyloxy,butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy,nonenyloxy, or decenyloxy

“Alkynyloxy” means and includes an alkynyl containing at least onecarbon-oxygen single bond. Non-limiting examples may includepentynyloxy, hexynyloxy, heptynyloxy, octynyloxy, nonynyloxy, ordecynyloxy.

“Cycloalkoxy” means and includes a cycloalkyl containing at least onecarbon-oxygen single bond. Non-limiting examples may includecyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,cycloheptyloxy, cyclooctyloxy, cyclodecyloxy, norbornyloxy, orbicyclo[2.2.2]octyloxy.

“Cyclohaloalkyl” means and includes a monocyclic or polycyclic,saturated substituent comprising carbon, halogen, and hydrogen.Non-limiting examples may include 1-chlorocyclopropyl,1-chlorocyclobutyl, or 1-dichlorocyclopentyl.

“Cycloalkenyloxy” means and include a cycloalkenyl further consisting ofa carbon-oxygen single bond. Non-limiting examples may includecyclobutenyloxy, cyclopentenyloxy, cyclohexenyloxy, cycloheptenyloxy,cyclooctenyloxy, cyclodecenyloxy, norbornenyloxy, orbicyclo[2.2.2]octenyloxy.

“Alkylthio” means and includes an alkyl group containing at least onecarbon-sulfur single bond.

“Haloalkylthio” means and includes an alkyl group containing at leastone carbon-sulfur single bond and halogen atom.

“Halo” or “halogen” means and includes fluorine, chlorine, bromine, oriodine.

“Haloalkyl” means and includes an alkyl group substituted with at leastone halogen atom.

“Haloalkoxy” means and includes an alkoxy group substituted with atleast one halogen atom.

“Heteroatom” means and includes sulfur (S), oxygen (O), or nitrogen (N)atom.

“Heteroalkyl” means and includes an alkyl containing at least one sulfur(S), oxygen (O), or nitrogen (N) atom.

“Heterocyclyl” means a cyclic substituent that may be fully saturated,partially unsaturated, or fully unsaturated, where the cyclic structurecontains at least one carbon and at least one heteroatom, where saidheteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, thatatom can be in other oxidation states such as a sulfoxide and sulfone.Examples of aromatic heterocyclyls include, but are not limited to,benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,benzothienyl, benzothiazolyl, cinnolinyl, furanyl, imidazolyl,indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl,oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl,quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl,triazinyl, and triazolyl. Examples of fully saturated heterocyclylsinclude, but are not limited to, piperazinyl, piperidinyl, morpholinyl,pyrrolidinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl andtetrahydropyranyl. Examples of partially unsaturated heterocyclylsinclude, but are not limited to, 1,2,3,4-tetrahydroquinolinyl,4,5-dihydro-oxazolyl, 4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl,and 2,3-dihydro-[1,3,4]-oxadiazolyl. Additional examples include thefollowing

“Pesticidally effective amount” means and includes an amount of activematerial that causes an adverse effect to the at least one insect,wherein the adverse effect may include deviations from naturaldevelopment, killing, regulation, or the like.

“Control” or grammatical variations thereof means and includesregulating the number of living insects or regulating the number ofviable eggs of the insects, or both.

“Synergistic effect” or grammatical variations thereof means andincludes a cooperative action encountered in a combination of two ormore active agents in which the combined activity of the two or moreactive agents exceeds the sum of the activity of each active agentalone.

Pesticidal Compounds

In one particular embodiment, a pesticidal composition comprises acompound of formula I, or any agriculturally acceptable salt thereof:

wherein:

R₁, R₂, and R₄ are independently hydrogen, F, Cl, Br, I, substituted orunsubstituted C₁-C₆ alkyl, or substituted or unsubstituted C₁-C₆haloalkyl, C₃-C₁₀ cycloalkyl, or C₃-C₁₀ halocycloalkyl, C₂-C₆ alkenyl,C₂-C₆ alkynyl, wherein each said R₁, R₂, and R₄, when substituted, hasone or more substituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆ haloalkyl, C₃-C₁₀ cycloalkyl,or C₃-C₁₀ halocycloalkyl, each of which may be substituted and mayoptionally be substituted with R₁₀;

R₃ is hydrogen, F, Cl, Br, I, CN, NO₂, substituted or unsubstitutedC₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl, C₂-C₆ alkynyl,substituted or unsubstituted C₁-C₆ alkoxy, substituted or unsubstitutedC₃-C₁₀ cycloalkyl, substituted or unsubstituted C₁-C₆ haloalkyl,substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₁-C₂₀ heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀, C(═X₁)N(R₁₀)₂,N(R₁₀)₂, N(R₁₀)C(═X₁)R₁₀, SR₁₀, S(O)_(n)OR₁₀, or R₁₀S(O)_(n)R₁₀, whereineach said R₃, when substituted, has one or more substituents selectedfrom F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀aryl, or C₁-C₂₀ heterocyclyl, each of which may be substituted, and mayoptionally be substituted with R₁₀;

R₅ is selected from hydrogen, F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₁-C₆ alkoxy, C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₁-C₂₀ heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀, C(═X₁)N(R₁₀)₂,N(R₁₀)₂, N(R₁₀)C(═X₁)R₁₀, S(O)_(n)R₁₀, S(O)_(n)OR₁₀, or R₁₀S(O)_(n)R₁₀,wherein each said R₅, when substituted, has one or more substituentsselected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy,C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, each of which may be substituted, and may optionally besubstituted with R₁₀;

Y is a bond or is substituted or unsubstituted C₁-C₆ alkyl, orsubstituted or unsubstituted C₂-C₆ alkenyl,

Except where Y is a bond, wherein each Y, when substituted, has one ormore substituents selected from hydrogen, F, Cl, Br, I, CN, NO₂, C₁-C₆alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆haloalkyloxy, or C₃-C₁₀ cycloalkyl; optionally Y and R₇ may be connectedin a cyclic arrangement, where optionally such arrangement may have oneor more heteroatoms selected from O, S, or N, in the cyclic structureconnecting Y and R₇;

R₆ is selected from hydrogen, substituted or unsubstituted C₁-C₆ alkyl,substituted or unsubstituted C₂-C₆ alkenyl, substituted or unsubstitutedC₂-C₆ alkynyl, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₁-C₂₀ heterocyclyl, C₁-C₆ alkyl C₆-C₂₀ aryl (wherein the alkyl and arylcan independently be substituted or unsubstituted), C₁-C₆ alkyl-(C₃-C₁₀cyclohaloalkyl) wherein the alkyl and cyclohaloalkyl can independentlybe substituted or unsubstituted, or C₁-C₆ alkyl-(C₃-C₁₀ cycloalkyl)wherein the alkyl and cycloalkyl may independently be substituted orunsubstituted, bauwherein each R₆, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₂-C₆haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, C₁-C₂₀ heterocyclyl,or R₁₀ aryl, each of which may be substituted, and may optionally besubstituted with R₁₀;

R₇ is R₉ or R₈S(O)_(n)R₉;

R₈ is substituted or unsubstituted C₂-C₁₂ alkenyl, substituted orunsubstituted C₁-C₁₂ alkyl, substituted or unsubstituted C₃-C₁₀cycloalkyl, or substituted or unsubstituted C₁-C₁₀ heterocyclyl, whereineach said R₈, when substituted, has one or more substituents selectedfrom F, Cl, Br, I, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₃-C₁₀cycloalkyl, C₃-C₁₀ halocycloalkyl, OR₁₀, S(O)_(n)R₁₀, C₆-C₂₀ aryl, orC₁-C₂₀ heterocyclyl, each of which may be substituted, and mayoptionally be substituted with R₁₀;

R₉ is selected from hydrogen, substituted or unsubstituted C₁-C₆ alkyl,substituted or unsubstituted C₂-C₆ alkenyl, substituted or unsubstitutedC₁-C₆ alkoxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted haloalkyl, substituted or unsubstitutedC₃-C₁₀ halocycloalkyl, substituted or unsubstituted C₃-C₁₀ cycloalkenyl,substituted or unsubstituted C₆-C₂₀ aryl, or substituted orunsubstituted C₁-C₂₀ heterocyclyl, wherein each said R₉, whensubstituted, has one or more substituents selected from F, Cl, Br, I,CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆ haloalkyl,C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₁-C₆ haloalkyloxy, C₂-C₆haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀halocycloalkyl, C₃-C₁₀ halocycloalkenyl, oxo, OR₁₀, S(O)_(n)R₁₀, C₆-C₂₀aryl, or C₁-C₂₀ heterocyclyl, each of which may be substituted, and mayoptionally be substituted with R₁₀;

R₁₀ is selected from hydrogen, CN, substituted or unsubstituted C₁-C₆alkyl, substituted or unsubstituted C₂-C₆ alkenyl, substituted orunsubstituted C₁-C₆ alkoxy, substituted or unsubstituted C₂-C₆alkenyloxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl, substitutedor unsubstituted C₃-C₁₀ cycloalkenyl, substituted or unsubstitutedC₆-C₂₀ aryl, substituted or unsubstituted C₁-C₂₀ heterocyclyl,substituted or unsubstituted S(O)_(n)C₁-C₆ alkyl, or substituted orunsubstituted N(C₁-C₆alkyl)₂, wherein each said R₁₀, when substituted,has one or more substituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OC₁-C₆alkyl, OC₁-C₆ haloalkyl, S(O)_(n)C₁-C₆alkyl, S(O)_(n)OC₁-C₆ alkyl,C₆-C₂₀ aryl, or C₁-C₂₀ heterocyclyl;

Q and X₁ are independently oxygen (O) or sulfur (S);

-   -   n is 0, 1, or 2; and

Z is N or C—R₃.

In another embodiment, R₁, R₂, and R₄ are hydrogen.

In another embodiment R₃ is hydrogen, F, Cl, Br, or I, preferablyhydrogen or F.

In another embodiment, R₅ is selected from F, Cl, Br, I, orunsubstituted C₁-C₆ alkyl, preferably, Cl or CH₃.

In another embodiment, Y—C≡C—R₆ is CH₂C≡CH or CH(CH₃)C≡CH.

In another embodiment, R₇ is (C₁-C₆)alkylS(O)_(n)(C₁-C₆)alkyl,(C₁-C₆)alkylS(O)_(n)(C₁-C₆)haloalkyl, or(C₁-C₆)alkylS(O)_(n)(C₁-C₆)alkyl(C₃-C₆)halocycloalkyl.

Q and X₁ are independently oxygen (O).

n is 0 or 1.

Z is C—R₃.

In one embodiment, the compound of formula I (where Y is substituted orunsubstituted C₁-C₆ alkyl, or substituted or unsubstituted C₂-C₆alkenyl) may be prepared as shown in Scheme 1.

In step a of Scheme 1, a tert-butoxy carbamate compound 1-1 (prepared asdescribed in the PCT Application No. WO 2010/129497A1) may be treatedwith a base in an aprotic solvent at a temperature from about −78° C. toabout 120° C., followed by reaction with an electrophile 1-2, wherein LGmay be a halogen, such as Cl, Br and I, or an alkyl or aryl sulfonate,and wherein Y is substituted or unsubstituted C₁-C₆ alkyl, orsubstituted or unsubstituted C₂-C₆ alkenyl, to afford a thiazolecompound 1-3. Non-limiting examples of suitable aprotic solvents mayinclude N,N-dimethylformamide (DMF), tetrahydrofuran (THF), dioxane,dimethylsulfoxide (DMSO), diglyme, monoglyme, or N-methylpyrrolidinone(NMP). Non-limiting examples of suitable bases may include sodiumhydride, potassium tert-butoxide, alkyl lithium reagents such astert-BuLi, n-BuLi and alkylmagnesium halides, or other metal hydrides.

In step b of Scheme 1, the thiazole compound 1-3 may be reacted withacid, such as hydrogen chloride (HCl), in a solvent, such as dioxane, toafford the corresponding salt such as HCl salt 1-4. Non-limitingexamples of other suitable acids may include trifluoroacetic acid (TFA),hydrogen bromide (HBr), or mineral acids such as sulfuric acid (H₂SO₄).

In step c of Scheme 1, the amines 1-4 may be treated with an acidchloride or an acid anhydride 1-5 in the presence of a base, such astriethylamine, or N,N′-4-dimethylaminopyridine (DMAP) in an aproticsolvent, such as methylene chloride (CH₂Cl₂), at a temperature fromabout −80° C. to about 100° C. to provide the corresponding compounds ofthe formula (I). Non-limiting examples of other suitable bases mayinclude Hünig's base, metal hydrides, or alkali hydroxides.

Alternatively, in step c of Scheme 1, the thiazoles 1-4 may be treatedwith an acid compound 1-5, where X is OH, in the presence of an amidecoupling agent, such as 1-(3-dimethylaminopropyl)-3-ethylcarbodiimidehydrochloride (EDC), dicyclohexyl carbodiimide (DCC) or diisopropylcarbodiimide (DIC), and a base, such as DMAP or triethylamine, in anaprotic solvent, such as CH₂Cl₂ or DMF, to provide the compounds offormula I.

In one embodiment, the compound of formula 2-6 (where Z is N, CH or CF,R₅ is methyl or Cl, and R₆ is hydrogen or methyl, n′ is 1 or 2) may beprepared as shown in Scheme 2.

The tert-butoxy carbamate compound (2-1) may be prepared as described inthe PCT Application No. WO 2010/129497A1, where Z is CF, R₅ is methyl orCl. The tert-butoxy carbamates (2-1) may be prepared as described in thePCT Application No. WO 2010/129497A1, where Z is CH and R₅ is methyl.The tert-butoxy carbamates (2-1) may be prepared according to Scheme 4,where Z is CH and R₅ is Cl. The tert-butoxy carbamates (2-1) may beprepared as described in the PCT Application No. WO 2010/129497A1, whereZ is N and R₅ is methyl. The tert-butoxy carbamates (2-1) may beprepared as described in the PCT Application No. WO 2010/129497A1 orScheme 4, where Z is N and R₅ is Cl.

In step a of Scheme 2, one equivalent of the tert-butoxy carbamatecompound (2-1) (Z=N, CH, or CF; R₅=Me or Cl) may be treated with a base,such as sodium hydride (from about 0.9 eq to about 1.2 eq), in anaprotic solvent, such as DMF (at concentrations between about 0.01 M toabout 4 M), at a temperature from about −78° C. to about 120° C.,followed by addition of an electrophile (2-2), wherein R₆ is hydrogen ormethyl (about 0.9 eq to about 4 eq), and wherein LG may be a halogen,such as Cl, Br and I, or a mesylate or other leaving groups, to providethe amide compound (2-3) (Z=N, CH, or CF; R₅=Me or Cl; R₆=H or Me).Non-limiting examples of other suitable solvents may include THF,dioxane, DMSO, diglyme, monoglyme, or NMP. Non-limiting examples ofother suitable bases may include potassium tert-butoxide, alkyl lithiumreagents such tert-BuLi, n-BuLi, alkyl magnesium halides, or other metalhydrides.

In step b of Scheme 2, one equivalent of the amide compound (2-3) (Z=Nor CH or CF; R₅=Me or Cl; R₆=H or Me) may be treated with an acid suchas HCl (from about 1 mol eq and to about 100 mol eq) in a solvent suchas dioxane (at a concentration between about 0.001 M to about 10 M) toprovide the corresponding HCl salt (2-4) (Z=N, CH, or CF; R₅=Me or Cl;R₆=H or Me). Non-limiting examples of other suitable acids may includeTFA, HBr, or mineral acids such as H₂SO₄. It is appreciated that the HClsalt (2-4) may be free base and that the resultant amine may be suitablefor subsequent chemical operations.

In step c of Scheme 2, the HCl salt (2-4) (Z=N, CH, or CF; R₅=Me or Cl,R₆=H or Me) may be treated with about 1 eq to about 4 eq of 2-5, where xis Cl, in the presence of a base such as triethylamine (from about 2 eqto about 10 eq) in an aprotic solvent such as CH₂Cl₂ (at concentrationsbetween about 0.001 M to about 5 M) at a temperature from about −80° C.to about 100° C. to provide the corresponding amide compound (2-6).Non-limiting examples of other suitable bases may include Hünig's base,metal hydrides, or metal hydroxides.

In one embodiment, the compound of formula 3-2 may be prepared as shownin Scheme 3.

In step a of Scheme 3, the sulfoxide or sulfone compound 3-1 (Z=N, CH,or CF; R₅=Me or Cl; R₆=Me or H; n=1 or 2; n′=1 or 2) may be prepared byreacting one equivalent of corresponding sulfide compound 2-6 (Z=N, CH,or CF; R₅=Me or Cl, n′=1 or 2) with about 1 eq or about 2.0 to 2.5 eq,respectively, of an oxidant such as NaBO₃.4H₂O in a solvent such asacetic acid (between a concentration of about 0.001 M to 2 M) at atemperature from about −20° C. to 120° C. as described in the PCTApplication No. WO 2010/129497A1.

In step c of Scheme 3, the amide compound 2-6 (Z=N, CH, or CF; R₅=Me orCl, R₆=H or Me; n′=1, 2) may be converted to the corresponding thioamidecompound 3-2 (Z=N, CH or CF; R₅=Me or Cl, R₆=H or Me; n′=1 or 2) byreacting with a source of sulfur such as Lawesson's reagent (from about1 eq to about 10 eq) in a presence of a solvent such as diglyme (at aconcentration between about 0.001 M to about 5 M) at a temperature fromabout −20° C. to about 200° C.

Alternatively, as shown in step b of Scheme 3, the sulfoxide or sulfone3-1 (Z=N, CH, or CF; R₅=Me or Cl, R₆=H, Me; n=1 or 2; n′=1 or 2) may betreated with a source of sulfur such as Lawesson's reagent (from about 1eq to about 10 eq) in a presence of a solvent such as diglyme (at aconcentration between about 0.001 M to about 5 M) at a temperature offrom about −20° C. to about 200° C. to provide thioamide compound 3-3(Z=N, CH, or CF; R₅=Me or Cl, R₆=H or Me; n=1 or 2; n′=1 or 2).

In one embodiment, the compound of formula 1A may be prepared as shownin Scheme 4.

In step a of Scheme 4, thiazole compound C1 may be prepared by reactingthiazole compound C0 with a chlorination reagent such asN-chlorosuccinimide in a solvent, such as acetonitrile at a temperatureof about 65° C.

In step b of Scheme 4, one of the Boc-protecting group of compound C1may be removed by treating with an acid such as trifluoroacetic acid(TFA) in a polar aprotic solvent such as CH₂Cl₂ at ambient temperatureto provide thiazole compound C2.

In step c of Scheme 4, thiazole compound C3 may be prepared by reactingthe N-Boc-protected carbamate compound C2 in a polar aprotic solventsuch as DMF with a base such as sodium hydride and then an electrophilesuch as 3-bromoprop-1-yne, at a temperature from about −20° C. to about50° C.

In step d of Scheme 4, the Boc protecting group of thiazole compound C3may be removed by treating with a strong acid such as hydrochloric acidin dioxane to provide a corresponding salt such as an HCl salt, of4-chloro-N-(prop-2-yn-1-yl)-2-(pyridin-3-yl) thiazol-5-amine (C4).

In step e of Scheme 4, the 4-chloro-N-(prop-2-yn-1-yl)-2-(pyridin-3-yl)thiazol-5-amine HCl salt (C4) may be reacted with3-(methylthio)propanoyl chloride in a solvent such as tetrahydrofuran(THF) in the presence of a base such as DMAP, at a temperature fromabout −20° C. to about 60° C., to provide the compound (IA).

In one embodiment, the compound of formula 1-3 may be prepared as shownin Scheme 5.

In step a of Scheme 5, an acid compound of the formula 5-1 (wherein R₅is Me or Cl) may be treated with diphenylphosphoryl azide (DPPA) and abase such as triethylamine in an aprotic solvent, such as toluene, atroom temperature to afford the corresponding acylazide 5-2. In step b ofScheme 5, acyl azide of the formula 5-2 may be heated to about 100° C.in the presence of a an alcohol, such as tert-butanol, to give thecorresponding tert-butyl carbamate of the formula 5-3. In Step c ofScheme 5, tert-butyl carbamates of the formula 5-3 may be treated with abase in an aprotic solvent at a temperature from about −78° C. to about120° C., followed by reaction with an electrophile 1-2, wherein LG maybe a halogen, such as Cl, Br and I, or an alkyl or aryl sulfonate, toafford a thiazole compound 5-4. Non-limiting examples of suitableaprotic solvents may include N,N-dimethylformamide (DMF),tetrahydrofuran (THF), dioxane, dimethylsulfoxide (DMSO), diglyme,monoglyme, or N-methylpyrrolidinone (NMP). Non-limiting examples ofsuitable bases may include sodium hydride, potassium tert-butoxide,alkyl lithium reagents such as tert-BuLi, n-BuLi and alkylmagnesiumhalides, or other metal hydrides. In step d of Scheme 5, the thiazolecompounds of formula 5-4, wherein R5 and R6 are as previously defined,may be allowed to react under Suzuki coupling conditions with a boronicacid of formula 5-5, wherein Z, R1, R2 and R4 are as previously defined,to provide the thiazoles of formula 1-3.

Pesticidally Acceptable Acid Addition Salts, Salt Derivatives, Solvates,Ester Derivatives, Polymorphs, Isotopes, Radionuclides and Stereoisomers

In some embodiments, the compound of formula I may be formulated intopesticidally acceptable acid addition salts. By way of a non-limitingexample, an amine function can form salts with hydrochloric,hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic,salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic,ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic,ethanesulfonic, hydroxymethanesulfonic, hydroxyethanesulfonic, andtrifluoroacetic acids. Additionally, by way of a non-limiting example,an acid function can form salts including those derived from alkali oralkaline earth metals and those derived from ammonia and amines.Examples of preferred cations include sodium, potassium, and magnesium.

In some embodiments, the compound of formula I may be formulated intosalt derivatives. By way of a non-limiting example, a salt derivativecan be prepared by contacting a free base with a sufficient amount ofthe desired acid to produce a salt. A free base may be regenerated bytreating the salt with a suitable dilute aqueous base solution such asdilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia,and sodium bicarbonate. As an example, in many cases, a pesticide, suchas 2,4-D, is made more water-soluble by converting it to itsdimethylamine salt.

In further embodiments, the compound of formula I may be formulated intostable complexes with a solvent, such that the complex remains intactafter the non-complexed solvent is removed. These complexes are oftenreferred to as “solvates.” However, it is particularly desirable to formstable hydrates with water as the solvent.

In some embodiments, the compound of formula I may be made into esterderivatives. These ester derivatives can then be applied in the samemanner as the invention disclosed in this document is applied.

In some embodiments, the compound of formula I may be made as variouscrystal polymorphs. Polymorphism is important in the development ofagrochemicals since different crystal polymorphs or structures of thesame molecule can have vastly different physical properties andbiological performances.

In further embodiments, the compound of formula I may be made withdifferent isotopes. Of particular importance are molecules having ²H(also known as deuterium) in place of ¹H.

In some embodiments, the compound of formula I may be made withdifferent radionuclides. Of particular importance are molecules having¹³C or ¹⁴C.

In some embodiments, the e compound of formula I may exist as one ormore stereoisomers. Thus, certain molecules can be produced as racemicmixtures. It will be appreciated by those skilled in the art that onestereoisomer may be more active than the other stereoisomers. Individualstereoisomers may be obtained by known selective synthetic procedures,by conventional synthetic procedures using resolved starting materials,or by conventional resolution procedures. Certain molecules disclosed inthis document can exist as two or more isomers. The various isomersinclude geometric isomers, diastereomers, and enantiomers. Thus, themolecules disclosed in this document include geometric isomers, racemicmixtures, individual stereoisomers, and optically active mixtures. Itwill be appreciated by those skilled in the art that one isomer may bemore active than the others. The structures disclosed in the presentdisclosure are drawn in only one geometric form for clarity, but areintended to represent all geometric forms of the molecule.

Pesticidal Compositions

In one particular embodiment, a pesticidal composition comprises thecompound of formula I, or any agriculturally acceptable salt thereof.

In some embodiments, a pesticidal composition comprises the compound offormula I or any agriculturally acceptable salt thereof, and aphytologically-acceptable inert carrier (e.g., solid carrier, or liquidcarrier).

In one embodiment, the pesticidal composition may further comprise atleast one additive selected from surfactant, a stabilizer, an emeticagent, a disintegrating agent, an antifoaming agent, a wetting agent, adispersing agent, a binding agent, dyes, or fillers.

In some embodiments, the pesticidal compositions may be in the form ofsolid. Non-limiting examples of the solid forms may include power, dustor granular formulations.

In other embodiments, the pesticidal compositions may be in the form ofliquid formulation. Examples of the liquid forms may include, but notlimited to, dispersion, suspension, emulsion or solution in appropriateliquid carrier.

In further embodiments, the pesticidal compositions may be in the formof liquid dispersion, wherein the compound of formula I may be dispersedin water or other agriculturally suitable liquid carrier.

In yet further embodiments, the pesticidal compositions may be in theform of solution in an appropriate organic solvent. In one embodiment,the spray oils, which are widely used in agricultural chemistry, may beused as an organic solvent for the pesticidal compositions.

The pesticidal composition may be used in conjunction (such as, in acompositional mixture, or a simultaneous or sequential application) withone or more compounds having acaricidal, algicidal, avicidal,bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal,nematicidal, rodenticidal, and/or virucidal properties.

Furthermore, the pesticidal composition may be used in conjunction (suchas, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more compounds that are antifeedants, birdrepellents, chemosterilants, herbicide safeners, insect attractants,insect repellents, mammal repellents, mating disrupters, plantactivators, plant growth regulators, and/or synergists.

Insecticides

Non-limiting examples of insecticides that may be used in combinationwith the compound of formula I may include 1,2-dichloropropane,abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin,acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin,allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone,α/p/ω-endosulfan, amidithion, aminocarb, amiton, amiton oxalate,amitraz, anabasine, athidathion, azadirachtin, azamethiphos,azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate,barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin,zeta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin,biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos,bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb,buprofezin, butacarb, butathiofos, butocarboxim, butonate,butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide,camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbontetrachloride, carbophenothion, carbosulfan, cartap, cartaphydrochloride, chlorantraniliprole, chlorbicyclen, chlordane,chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos,chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform,chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos,chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerinII, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copperacetoarsenite, copper arsenate, copper naphthenate, copper oleate,coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite,cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin,cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin,cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion,demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon,diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin,diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate,dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop,dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion,disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin,emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin,EPN, epofenonane, eprinomectin, esdépalléthrine, esfenvalerate, etaphos,ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethylformate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethyleneoxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid,flubendiamide (additionally resolved isomers thereof), flucofuron,flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox,fluvalinate, fonofos, formetanate, formetanate hydrochloride,formothion, formparanate, formparanate hydrochloride, fosmethilan,fospirate, fosthietan, fufenozide, furathiocarb, furethrin,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin,indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos,isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane,isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos,juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan,mercurous chloride, mesulfenfos, metaflumizone, methacrifos,methamidophos, methidathion, methiocarb, methocrotophos, methomyl,methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide,methyl isothiocyanate, methylchloroform, methylene chloride,metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate,milbemectin, milbemycin oxime, mipafox, mirex, molosultap,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene,parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin,phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl,pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassiumarsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I,precocene II, precocene III, primidophos, profenofos, profluralin,profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur,prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,silafluofen, silica gel, sodium arsenite, sodium fluoride, sodiumhexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad,spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid,sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate,tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin,theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime,thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat,trifenofos, triflumuron, trimethacarb, triprene, vamidothion,vaniliprole, XMC, xylylcarb, zeta-cypermethrin, or zolaprofos.

Acaricides

Non-limiting examples of acaricides that may be used in combination withthe compound of formula I may include acequinocyl, amidoflumet, arsenousoxide, azobenzene, azocyclotin, benomyl, benoxafos, benzoximate, benzylbenzoate, bifenazate, binapacryl, bromopropylate, chinomethionat,chlorbenside, chlorfenethol, chlorfenson, chlorfensulphide,chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate,clofentezine, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid,dicofol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4,dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylsulfone, disulfiram, dofenapyn, etoxazole, fenazaquin, fenbutatin oxide,fenothiocarb, fenpyroximate, fenson, fentrifanil, fluacrypyrim,fluazuron, flubenzimine, fluenetil, flumethrin, fluorbenside,hexythiazox, mesulfen, MNAF, nikkomycins, proclonol, propargite,quintiofos, spirodiclofen, sulfiram, sulfur, tetradifon, tetranactin,tetrasul, or thioquinox.

Nematicides

Non-limiting examples of nematicides that may be used in combinationwith the compound of formula I may include 1,3-dichloropropene,benclothiaz, dazomet, dazomet-sodium, DBCP, DCIP, diamidafos,fluensulfone, fosthiazate, furfural, imicyafos, isamidofos, isazofos,metam, metam-ammonium, metam-potassium, metam-sodium, phosphocarb, orthionazin.

Fungicides

Non-limiting examples of fungicides that may be used in combination withthe compound of formula I may include (3-ethoxypropyl)mercury bromide,2-methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinolinesulfate, 8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-S-methyl,acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol,ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin,azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl,benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb,benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril,benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin,binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S,Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture,buthiobate, butylamine, calcium polysulfide, captafol, captan,carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshuntmixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil,chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin,chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole,copper acetate, copper carbonate, basic, copper hydroxide, coppernaphthenate, copper oleate, copper oxychloride, copper silicate, coppersulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprousoxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil,cypendazole, cyproconazole, cyprodinil, dazomet, dazomet-sodium, DBCP,debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone,dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine,diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate,difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin,diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine,dipyrithione, disulfiram, ditalimfos, dithianon, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorphbenzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edifenphos,epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate,ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate,etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydroxide,ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph,fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin,fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil,flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl,fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil,furconazole, furconazole-cis, furfural, furmecyclox, furophanate,glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene,hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen,hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole,iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate,iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb,isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin,kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil,mecarbinzid, mepanipyrim, mepronil, meptyldinocap, mercuric chloride,mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole,methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate,methylmercury benzoate, methylmercury dicyandiamide, methylmercurypentachlorophenoxide, metiram, metominostrobin, metrafenone,metsulfovax, milneb, myclobutanil, myclozolin,N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin,nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace,orysastrobin, oxadixyl, oxine-copper, oxpoconazole, oxpoconazolefumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercuryacetate, phenylmercury chloride, phenylmercury derivative ofpyrocatechol, phenylmercury nitrate, phenylmercury salicylate,phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate,polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassiumpolysulfide, potassium thiocyanate, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propiconazole,propineb, proquinazid, prothiocarb, prothiocarb hydrochloride,prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril,pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor,pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole,quinoxyfen, quintozene, rabenzazole, salicylanilide, sedaxane,silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide,sodium pentachlorophenoxide, sodium polysulfide, spiroxamine,streptomycin, sulfur, sultropen, TCMTB, tebuconazole, tebufloquin,tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole,thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal,thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid,tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon,triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltinoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin,triflumizole, triforine, triticonazole, uniconazole, uniconazole-P,validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate,zineb, ziram, or zoxamide.

Herbicides

Non-limiting examples of herbicides that may be used in combination thecompound of formula I may include 2,3,6-TBA, 2,3,6-TBA-dimethylammonium,2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl,2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl,2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl,2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl,2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl,2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium,2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium,2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA, 3,4-DB,3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen,acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein, alachlor,allidochlor, alloxydim, alloxydim-sodium, allyl alcohol, alorac,ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,aminocyclopyrachlor, aminocyclopyrachlor-methyl,aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium,aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl, amitrole,ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium,asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne,barban, BCPC, beflubutamid, benazolin, benazolin-dimethylammonium,benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin,benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone,bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzoylprop-ethyl,benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium,bispyribac, bispyribac-sodium, borax, bromacil, bromacil-lithium,bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil,bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate,bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos,butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon,butylate, cacodylic acid, cafenstrole, calcium chlorate, calciumcyanamide, cambendichlor, carbasulam, carbetamide, carboxazole,carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen,chloramben, chloramben-ammonium, chloramben-diolamine,chloramben-methyl, chloramben-methylammonium, chloramben-sodium,chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenac-sodium,chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol,chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil,chlorprocarb, chlorpropham, chlorsulfuron, chlorthal,chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl,cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate,clodinafop, clodinafop-propargyl, clofop, clofop-isobutyl, clomazone,clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,clopyralid-olamine, clopyralid-potassium,clopyralid-tris(2-hydroxypropyl)ammonium, cloransulam,cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol,cumyluron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron,cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquatchloride, cyprazine, cyprazole, cypromid, daimuron, dalapon,dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet,dazomet-sodium, delachlor, desmedipham, desmetryn, di-allate, dicamba,dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium,dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium,dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, dichlorprop,dichlorprop-2-ethylhexyl, dichlorprop-butotyl,dichlorprop-dimethylammonium, dichlorprop-ethylammonium,dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,dichlorprop-P-dimethylammonium, dichlorprop-potassium,dichlorprop-sodium, diclofop, diclofop-methyl, diclosulam, diethamquat,diethamquat dichloride, diethatyl, diethatyl-ethyl, difenopenten,difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate,diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron,dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine,dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate,diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat dibromide,disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl,endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium,epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron,ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, ethoxyfen,ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD,fenasulam, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butometyl,fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl,fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P,fenoxaprop-P-ethyl, fenoxasulfone, fenteracol, fenthiaprop,fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA, ferrous sulfate,flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl,flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam,fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P,fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium,flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr,flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl,flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen,fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron,flupoxam, flupropacil, flupropanate, flupropanate-sodium,flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone,flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl,flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium,foramsulfuron, fosamine, fosamine-ammonium, furyloxyfen, glufosinate,glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium,glufosinate-P-sodium, glyphosate, glyphosate-diammonium,glyphosate-dimethylammonium, glyphosate-isopropylammonium,glyphosate-monoammonium, glyphosate-potassium, glyphosate-sesquisodium,glyphosate-trimesium, halosafen, halosulfuron, halosulfuron-methyl,haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P,haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium,hexachloroacetone, hexaflurate, hexazinone, imazamethabenz,imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic,imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin,imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr,imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iodobonil,iodomethane, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxyniloctanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone,iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate,isopropalin, isoproturon, isouron, isoxaben, isoxachlortole,isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen,lenacil, linuron, MAA, MAMA, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl,MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl,MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine,MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB,MCPB-ethyl, MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-isoctyl, mecoprop-methyl, mecoprop-P,mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium,mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb,medinoterb acetate, mefenacet, mefluidide, mefluidide-diolamine,mefluidide-potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl,mesotrione, metam, metam-ammonium, metamifop, metamitron,metam-potassium, metam-sodium, metazachlor, metazosulfuron, metflurazon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metolachlor,metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl,molinate, monalide, monisouron, monochloroacetic acid, monolinuron,monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA,naproanilide, napropamide, naptalam, naptalam-sodium, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone,oxyfluorfen, parafluron, paraquat, paraquat dichloride, paraquatdimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam,pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid,phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron,phenylmercury acetate, picloram, picloram-2-ethylhexyl,picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium,picloram-triethylammonium, picloram-tris(2-hydroxypropyl)ammonium,picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide,potassium cyanate, pretilachlor, primisulfuron, primisulfuron-methyl,procyazine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, proglinazine-ethyl, prometon, prometryn, propachlor,propanil, propaquizafop, propazine, propham, propisochlor,propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide,prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodium,prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl,pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl,pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate,pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac,pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac,quinoclamine, quinonamid, quizalofop, quizalofop-ethyl, quizalofop-P,quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron,saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine,simeton, simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide,sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron,sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, swep,TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron,thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone,tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron,tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl,triclopyr-ethyl, triclopyr-triethylammonium, tridiphane, trietazine,trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron,triflusulfuron-methyl, trifop, trifop-methyl, trifopsime,trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron,vernolate, or xylachlor.

Biopesticides

The compound of formula I may also be used in combination (such as in acompositional mixture, or a simultaneous or sequential application) withone or more biopesticides. The term “biopesticide” is used for microbialbiological pest control agents that are applied in a similar manner tochemical pesticides. Commonly these are bacterial, but there are alsoexamples of fungal control agents, including Trichoderma spp. andAmpelomyces quisqualis (a control agent for grape powdery mildew).Bacillus subtilis are used to control plant pathogens. Weeds and rodentshave also been controlled with microbial agents. One well-knowninsecticide example is Bacillus thuringiensis, a bacterial disease ofLepidoptera, Coleoptera, and Diptera. Because it has little effect onother organisms, it is considered more environmentally friendly thansynthetic pesticides. Biological insecticides include products based on:

1. entomopathogenic fungi (e.g. Metarhizium anisopliae);

2. entomopathogenic nematodes (e.g. Steinernema feltiae); and

3. entomopathogenic viruses (e.g. Cydia pomonella granulovirus).

Other examples of entomopathogenic organisms include, but are notlimited to, baculoviruses, bacteria and other prokaryotic organisms,fungi, protozoa and Microsproridia. Biologically derived insecticidesinclude, but not limited to, rotenone, veratridine, as well as microbialtoxins; insect tolerant or resistant plant varieties; and organismsmodified by recombinant DNA technology to either produce insecticides orto convey an insect resistant property to the genetically modifiedorganism. In one embodiment, the molecules of Formula One may be usedwith one or more biopesticides in the area of seed treatments and soilamendments. The Manual of Biocontrol Agents gives a review of theavailable biological insecticide (and other biology-based control)products. Copping L. G. (ed.) (2004). The Manual of Biocontrol Agents(formerly the Biopesticide Manual) 3rd Edition. British Crop ProductionCouncil (BCPC), Farnham, Surrey UK.

Other Active Compounds

The compound of formula I may also be used in combination (such as in acompositional mixture, or a simultaneous or sequential application) withone or more of the following:

-   1.    3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   2.    3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone;-   4.    4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;-   5.    3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;-   6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;-   7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide;-   8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;-   9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide;-   10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide;-   11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;-   12. 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfonamide;-   13.    3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;-   14.    N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)    hydrazone;-   15.    N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)    hydrazone nicotine;-   16.    O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-methyl    thiocarbonate;-   17.    (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;-   18.    1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;-   19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl    mesylate; and-   20.    N-ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-α,    α,α-trifluoro-p-tolyl)hydrazone

The compound of formula I may also be used in combination (such as in acompositional mixture, or a simultaneous or sequential application) withone or more compounds in the following groups: algicides, antifeedants,avicides, bactericides, bird repellents, chemosterilants, herbicidesafeners, insect attractants, insect repellents, mammal repellents,mating disrupters, molluscicides, plant activators, plant growthregulators, rodenticides, or virucides.

Synergistic Mixtures and Synergists

The compound of formula I may be used in combination with at least oneother insecticides to form a synergistic mixture where the mode ofaction of such compounds compared to the mode of action of the compoundof formula I are the same, similar, or different. Examples of modes ofaction may include, but are not limited to: acetylcholinesteraseinhibitor; sodium channel modulator; chitin biosynthesis inhibitor;GABA-gated chloride channel antagonist; GABA and glutamate-gatedchloride channel agonist; acetylcholine receptor agonist; MET Iinhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholinereceptor; Midgut membrane disrupter; oxidative phosphorylationdisrupter, or ryanodine receptor (RyRs).

Additionally, the compound of formula I may be used in combination withat least one of fungicides, acaricides, herbicides or nematicides toform a synergistic mixture.

Furthermore, the compound of formula I may be used in combination withother active compounds, such as the compounds under the heading “OTHERACTIVE COMPOUNDS,” algicides, avicides, bactericides, molluscicides,rodenticides, virucides, herbicide safeners, adjuvants, and/orsurfactants to form a synergistic mixture. Moreover, the followingcompounds are known as synergists and may be used in combination withthe compound of formula I: piperonyl butoxide, piprotal, propyl isome,sesamex, sesamolin, sulfoxide, and tribufos.

Formulations

A pesticide is rarely suitable for application in its pure form. It isusually necessary to add other substances so that the pesticide can beused at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra low volume solutions. For further information onformulation types see “Catalogue of Pesticide Formulation Types andInternational Coding System” Technical Monograph no 2, 5th Edition byCropLife International (2002).

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations areeither solids, usually known as wettable powders, or water dispersiblegranules, or liquids usually known as emulsifiable concentrates, oraqueous suspensions. Wettable powders, which may be compacted to formwater dispersible granules, comprise an intimate mixture of thepesticide, a carrier, and surfactants. The concentration of thepesticide is usually from about 10% to about 90% by weight. The carrieris usually selected from among the attapulgite clays, themontmorillonite clays, the diatomaceous earths, or the purifiedsilicates. Effective surfactants, comprising from about 0.5% to about10% of the wettable powder, are found among sulfonated lignins,condensed naphthalenesulfonates, naphthalenesulfonates,alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants suchas ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are selected from conventionalanionic and non-ionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums may also be added, to increase the density andviscosity of the aqueous carrier. It is often most effective to grindand mix the pesticide at the same time by preparing the aqueous mixtureand homogenizing it in an implement such as a sand mill, ball mill, orpiston-type homogenizer.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier which has beenpre-formed to the appropriate particle size, in the range of from about0.5 to about 3 mm. Such compositions may also be formulated by making adough or paste of the carrier and compound and crushing and drying toobtain the desired granular particle size.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. They canbe applied as a seed dressing or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. They can be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By alteringthe chemistry of the polymer or by changing factors in the processing,microcapsules can be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which inturn, affects the residual performance, speed of action, and odor of theproduct.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having patent application Ser. No. 11/495,228.For ease of use, this embodiment will be referred to as “OIWE.”

For further information consult “Insect Pest Management” 2nd Edition byD. Dent, copyright CAB International (2000). Additionally, for moredetailed information consult “Handbook of Pest Control—The Behavior,Life History, and Control of Household Pests” by Arnold Mallis, 9thEdition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, when the compound of formula I or any agriculturallyacceptable salt thereof, are used in a formulation, such formulation canalso contain other components. These components include, but are notlimited to, (this is a non-exhaustive and non-mutually exclusive list)wetters, spreaders, stickers, penetrants, buffers, sequestering agents,drift reduction agents, compatibility agents, anti-foam agents, cleaningagents, and emulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulfate;sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface ofparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulfonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulfonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylarylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates. In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulfonates; sodium naphthalene sulfonate formaldehyde condensates;tristyrylphenol ethoxylate phosphate esters; aliphatic alcoholethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with twelve or more ethylene oxideunits and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved by the addition of a small amount of an EO-PO blockcopolymer surfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics, sorbitan monooleates, sorbitanmonooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alkyl ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, oil-in-water emulsions, suspoemulsions, and ultra lowvolume formulations, and to a lesser extent, granular formulations.Sometimes mixtures of solvents are used. The first main groups ofsolvents are aliphatic paraffinic oils such as kerosene or refinedparaffins. The second main group (and the most common) comprises thearomatic solvents such as xylene and higher molecular weight fractionsof C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful ascosolvents to prevent crystallization of pesticides when the formulationis emulsified into water. Alcohols are sometimes used as cosolvents toincrease solvent power. Other solvents may include vegetable oils, seedoils, and esters of vegetable and seed oils.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are not limited to,montmorillonite, bentonite, magnesium aluminum silicate, andattapulgite. Water-soluble polysaccharides have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum; carrageenam;alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC);hydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Thereforepreservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt; sorbic acid and its sodium or potassium salts;benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt;methyl p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations tofoam during mixing operations in production and in application through aspray tank. In order to reduce the tendency to foam, anti-foam agentsare often added either during the production stage or before fillinginto bottles. Generally, there are two types of anti-foam agents, namelysilicones and non-silicones. Silicones are usually aqueous emulsions ofdimethyl polysiloxane, while the non-silicone anti-foam agents arewater-insoluble oils, such as octanol and nonanol, or silica. In bothcases, the function of the anti-foam agent is to displace the surfactantfrom the air-water interface.

“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce theoverall environmental footprint of crop protection formulations. Greenagents are biodegradable and generally derived from natural and/orsustainable sources, e.g. plant and animal sources. Specific examplesare: vegetable oils, seed oils, and esters thereof, also alkoxylatedalkyl polyglucosides.

For further information, see “Chemistry and Technology of AgrochemicalFormulations” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “Insecticides in Agriculture andEnvironment—Retrospects and Prospects” by A. S. Perry, I. Yamamoto, I.Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

Pesticidal Activities

The disclosed pesticidal compositions may be used, for example, asnematicides, acaricides, pesticides, insecticides, miticides, and/ormolluscicides.

In one particular embodiment, a method of controlling pests comprisesapplying a pesticidal composition comprising a compound of formula I orany agriculturally acceptable salt thereof near a population of pests.

The compounds of formula I are generally used in amounts from about 0.01grams per hectare to about 5000 grams per hectare to provide control.Amounts from about 0.1 grams per hectare to about 500 grams per hectareare generally preferred, and amounts from about 1 gram per hectare toabout 50 grams per hectare are generally more preferred.

The area to which the compound of formula I is applied can be any areainhabited (or maybe inhabited, or traversed by) a pest, for example:where crops, trees, fruits, cereals, fodder species, vines, turf andornamental plants, are growing; where domesticated animals are residing;the interior or exterior surfaces of buildings (such as places wheregrains are stored), the materials of construction used in building (suchas impregnated wood), and the soil around buildings. Particular cropareas to use a molecule of Formula One include areas where apples, corn,sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley,oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes,peppers, crucifers, pears, tobacco, almonds, sugar beets, beans andother valuable crops are growing or the seeds thereof are going to beplanted. It is also advantageous to use ammonium sulfate with thecompound of formula I when growing various plants.

Controlling pests generally means that pest populations, pest activity,or both, are reduced in an area. This can come about when: pestpopulations are repulsed from an area; when pests are incapacitated inor around an area; or pests are exterminated, in whole, or in part, inor around an area. Of course, a combination of these results can occur.Generally, pest populations, activity, or both are desirably reducedmore than fifty percent, preferably more than 90 percent. Generally, thearea is not in or on a human; consequently, the locus is generally anon-human area.

The compound of formula I may be used in mixtures, appliedsimultaneously or sequentially, alone or with other compounds to enhanceplant vigor (e.g. to grow a better root system, to better withstandstressful growing conditions). Such other compounds are, for example,compounds that modulate plant ethylene receptors, most notably1-methylcyclopropene (also known as 1-MCP). Furthermore, such moleculesmay be used during times when pest activity is low, such as before theplants that are growing begin to produce valuable agriculturalcommodities. Such times include the early planting season when pestpressure is usually low.

The compound of formula I can be applied to the foliar and fruitingportions of plants to control pests. The molecules will either come indirect contact with the pest, or the pest will consume the pesticidewhen eating leaf, fruit mass, or extracting sap, that contains thepesticide. The compound of formula I can also be applied to the soil,and when applied in this manner, root and stem feeding pests can becontrolled. The roots can absorb a molecule taking it up into the foliarportions of the plant to control above ground chewing and sap feedingpests.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with, and/or be attracted to,the bait. Baits can also be applied to a surface of a building,(horizontal, vertical, or slant surface) where, for example, ants,termites, cockroaches, and flies, can come into contact with, and/or beattracted to, the bait. Baits can comprise a compound of formula I.

The compound of formula I can be encapsulated inside, or placed on thesurface of a capsule. The size of the capsules can range from nanometersize (about 100-900 nanometers in diameter) to micrometer size (about10-900 microns in diameter).

Because of the unique ability of the eggs of some pests to resistcertain pesticides, repeated applications of the compound of formula Imay be desirable to control newly emerged larvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying (for example, by sprayingan area) the compound of formula I to a different portion of the plant.For example, control of foliar-feeding insects can be achieved by dripirrigation or furrow application, by treating the soil with, forexample, pre- or post-planting soil drench, or by treating the seeds ofa plant before planting.

Seed treatment can be applied to all types of seeds, including thosefrom which plants genetically modified to express specialized traitswill germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensis orother insecticidal toxins, those expressing herbicide resistance, suchas “Roundup Ready” seed, or those with “stacked” foreign genesexpressing insecticidal toxins, herbicide resistance,nutrition-enhancement, drought resistance, or any other beneficialtraits. Furthermore, such seed treatments with the compound of formula Imay further enhance the ability of a plant to better withstand stressfulgrowing conditions. This results in a healthier, more vigorous plant,which can lead to higher yields at harvest time. Generally, about 1 gramof the compound of formula I to about 500 grams per 100,000 seeds isexpected to provide good benefits, amounts from about 10 grams to about100 grams per 100,000 seeds is expected to provide better benefits, andamounts from about 25 grams to about 75 grams per 100,000 seeds isexpected to provide even better benefits.

It should be readily apparent that the compound of formula I may be usedon, in, or around plants genetically modified to express specializedtraits, such as Bacillus thuringiensis or other insecticidal toxins, orthose expressing herbicide resistance, or those with “stacked” foreigngenes expressing insecticidal toxins, herbicide resistance,nutrition-enhancement, or any other beneficial traits.

The compound of formula I may be used for controlling endoparasites andectoparasites in the veterinary medicine sector or in the field ofnon-human animal keeping. The compound of formula I are applied, such asby oral administration in the form of, for example, tablets, capsules,drinks, granules, by dermal application in the form of, for example,dipping, spraying, pouring on, spotting on, and dusting, and byparenteral administration in the form of, for example, an injection.

The compound of formula I may also be employed advantageously inlivestock keeping, for example, cattle, sheep, pigs, chickens, andgeese. They may also be employed advantageously in pets such as, horses,dogs, and cats. Particular pests to control would be fleas and ticksthat are bothersome to such animals. Suitable formulations areadministered orally to the animals with the drinking water or feed. Thedosages and formulations that are suitable depend on the species.

The compound of formula I may also be used for controlling parasiticworms, especially of the intestine, in the animals listed above.

The compound of formula I may also be employed in therapeutic methodsfor human health care. Such methods include, but are limited to, oraladministration in the form of, for example, tablets, capsules, drinks,granules, and by dermal application.

Pests around the world have been migrating to new environments (for suchpest) and thereafter becoming a new invasive species in such newenvironment. The compound of formula I may also be used on such newinvasive species to control them in such new environment.

The compound of formula I may also be used in an area where plants, suchas crops, are growing (e.g. pre-planting, planting, pre-harvesting) andwhere there are low levels (even no actual presence) of pests that cancommercially damage such plants. The use of such molecules in such areais to benefit the plants being grown in the area. Such benefits, mayinclude, but are not limited to, improving the health of a plant,improving the yield of a plant (e.g. increased biomass and/or increasedcontent of valuable ingredients), improving the vigor of a plant (e.g.improved plant growth and/or greener leaves), improving the quality of aplant (e.g. improved content or composition of certain ingredients), andimproving the tolerance to abiotic and/or biotic stress of the plant.

Before a pesticide can be used or sold commercially, such pesticideundergoes lengthy evaluation processes by various governmentalauthorities (local, regional, state, national, and international).Voluminous data requirements are specified by regulatory authorities andmust be addressed through data generation and submission by the productregistrant or by a third party on the product registrant's behalf, oftenusing a computer with a connection to the World Wide Web. Thesegovernmental authorities then review such data and if a determination ofsafety is concluded, provide the potential user or seller with productregistration approval. Thereafter, in that locality where the productregistration is granted and supported, such user or seller may use orsell such pesticide.

The compound of formula I can be tested to determine its efficacyagainst pests. Furthermore, mode of action studies can be conducted todetermine if said molecule has a different mode of action than otherpesticides. Thereafter, such acquired data can be disseminated, such asby the interne, to third parties.

The disclosed pesticidal composition comprising a compound of formula Imay be used to control a wide variety of pests.

As a non-limiting example, in one or more embodiments, the method of thepresent disclosure may be used to control one or more members ofLyriomiza sativae, Caliothrips phaseoli, Paratrioza cockerel, Spodopteraexigua, Myzus persicae, Nilaparvata lugens, and Bemisia tabaci.

In additional embodiments, the method of the present disclosure may beused to control one or more members of at least one of PhylumArthropoda, Phylum Nematoda, Subphylum Chelicerata, Subphylum Myriapoda,Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla.In at least some embodiments, the method of the present disclosure maybe used to control one or more members of at least one of Class Insectaand Class Arachnida.

In further embodiments, the method of the present disclosure may be usedto control members of the Order Coleoptera (beetles) including, but notlimited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus(common bean weevil), Agrilus planipennis (emerald ash borer), Agriotesspp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle),Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidiusspp., Apion spp. (weevils), Apogonia spp. (grubs), Ataenius spretulus(Black Turfgrass Ataenius), Atomaria linearis (pygmy mangold beetle),Aulacophore spp., Bothynoderes punctiventris (beet root weevil), Bruchusspp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp.,Callosobruchus maculatus (southern cow pea weevil), Carpophilushemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp.,Cerotoma spp. (chrysomelids), Cerotoma trifurcata (bean leaf beetle),Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpodweevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp.(chrysomelids), Colaspis spp. (soil beetles), Conoderus scalaris,Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinusnitidis (Green June beetle), Crioceris asparagi (asparagus beetle),Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pusillus(flat grain beetle), Cryptolestes turcicus (Turkish grain beetle),Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp.(grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporausmarginatus (mango leaf-cutting weevil), Dermestes lardarius (larderbeetle), Dermestes maculates (hide beetle), Diabrotica spp.(chrysomelids), Epilachna varivestis (Mexican bean beetle), Faustinuscubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hyperapostica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana (chrysomelids), Phynchites spp.,Popillia japonica (Japanese beetle), Prostephanus truncates (largergrain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogusspp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp.(wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leafweevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granaryweevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstorebeetle), Tribolium spp. (flour beetles), Tribolium castaneum (red flourbeetle), Tribolium confusum (confused flour beetle), Trogodermavariabile (warehouse beetle), and Zabrus tenebioides.

In other embodiments, the method of the present disclosure may also beused to control members of the Order Dermaptera (earwigs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Dictyoptera (cockroaches)including, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Diptera (true flies) including, but isnot limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfablotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp.(fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp.(mosquitoes), Batrocera spp. (fruit flies), Bactrocera cucurbitae (melonfly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp. (fruitflies), Ceratitis capitata (Mediterranean fruit fly), Chrysops spp.(deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gallmidges), Culex spp. (mosquitoes), Dasineura spp. (gall midges),Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura(seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filthflies), Fannia canicularis (little house fly), Fannia scalaris (latrinefly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae,Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypodermalineatum (common cattle grub), Liriomyza spp. (leafminer flies),Liriomyza brassica (serpentine leafminer), Melophagus ovinus (sheepked), Musca spp. (muscid flies), Musca autumnalis (face fly), Muscadomestica (house fly), Oestrus ovis (sheep bot fly), Oscinella frit(frit fly), Pegomyia betae (beet leafminer), Phorbia spp., Psila rosae(carrot rust fly), Rhagoletis cerasi (cherry fruit fly), Rhagoletispomonella (apple maggot), Sitodiplosis mosellana (orange wheat blossommidge), Stomoxys calcitrans (stable fly), Tabanus spp. (horse flies),and Tipula spp. (crane flies).

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hemiptera (true bugs) including, but isnot limited to, Acrosternum hilare (green stink bug), Blissusleucopterus (chinch bug), Calocoris norvegicus (potato mind), Cimexhemipterus (tropical bed bug), Cimex lectularius (bed bug), Dagbertusfasciatus, Dichelops furcatus, Dysdercus suturellus (cotton stainer),Edessa meditabunda, Eurygaster maura (cereal bug), Euschistus heros,Euschistus servus (brown stink bug), Helopeltis antonii, Helopeltistheivora (tea blight plantbug), Lagynotomus spp. (stink bugs),Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp. (plant bugs),Lygus hesperus (western tarnished plant bug), Maconellicoccus hirsutus,Neurocolpus longirostris, Nezara viridula (southern green stink bug),Phytocoris spp. (plant bugs), Phytocoris californicus, Phytocorisrelativus, Piezodorus guildingi, Poecilocapsus lineatus (fourlined plantbug), Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea,and Triatoma spp. (bloodsucking conenose bugs/kissing bugs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Homoptera (aphids, scales,whiteflies, leaflhoppers) including, but is not limited to,Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodesproletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixusfloccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutellabigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii(California red scale), Aphis spp. (aphids), Aphis gossypii (cottonaphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove aphid),Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci(sweetpotato whitefly), Brachycolus noxius (Russian aphid),Brachycorynella asparagi (asparagus aphid), Brevennia rehi, Brevicorynebrassicae (cabbage aphid), Ceroplastes spp. (scales), Ceroplastes rubens(red wax scale), Chionaspis spp. (scales), Chrysomphalus spp. (scales),Coccus spp. (scales), Dysaphis plantaginea (rosy apple aphid), Empoascaspp. (leafhoppers), Eriosoma lanigerum (woolly apple aphid), Iceryapurchasi (cottony cushion scale), Idioscopus nitidulus (mangoleafhopper), Laodelphax striatellus (smaller brown planthopper),Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiae (potatoaphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae(rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarvafrimbiolata, Metopolophium dirhodum (rose grain aphid), Mictislongicornis, Myzus spp., Myzus persicae (green peach aphid), Nephotettixspp. (leafhoppers), Nephotettix cinctipes (green leafhopper),Nilaparvata lugens (brown planthopper), Parlatoria pergandii (chaffscale), Parlatoria ziziphi (ebony scale), Peregrinus maidis (corndelphacid), Philaenus spp. (spittlebugs), Phylloxera vitifoliae (grapephylloxera), Physokermes piceae (spruce bud scale), Planococcus spp.(mealybugs), Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pineapple mealybug), Quadraspidiotus perniciosus (San Jose scale),Rhapalosiphum spp. (aphids), Rhapalosiphum maida (corn leaf aphid),Rhapalosiphum padi (oat bird-cherry aphid), Saissetia spp. (scales),Saissetia oleae (black scale), Schizaphis graminum (greenbug), Sitobionavenae (English grain aphid), Sogatella furcifera (white-backedplanthopper), Therioaphis spp. (aphids), Toumeyella spp. (scales),Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies), Trialeurodesvaporariorum (greenhouse whitefly), Trialeurodes abutiloneus (bandedwingwhitefly), Unaspis spp. (scales), Unaspis yanonensis (arrowhead scale),and Zulia entreriana. In at least some embodiments, the method of thepresent disclosure may be used to control Myzus persicae.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hymenoptera (ants, wasps, and bees)including, but not limited to, Acromyrrmex spp., Athalia rosae, Attaspp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp.(sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant),Monomorium ssp., Monomorium minumum (little black ant), Monomoriumpharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp.(harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fireants), Tapoinoma sessile (odorous house ant), Tetranomorium spp.(pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp.(carpenter bees).

In certain embodiments, the method of the present disclosure may be usedto control members of the Order Isoptera (termites) including, but notlimited to, Coptotermes spp., Coptotermes curvignathus, Coptotermesfrenchii, Coptotermes formosanus (Formosan subterranean termite),Cornitermes spp. (nasute termites), Cryptotermes spp. (drywoodtermites), Heterotermes spp. (desert subterranean termites),Heterotermes aureus, Kalotermes spp. (drywood termites), Incistitermesspp. (drywood termites), Macrotermes spp. (fungus growing termites),Marginitennes spp. (drywood termites), Microcerotermes spp. (harvestertermites), Microtermes obesi, Procornitermes spp., Reticulitermes spp.(subterranean termites), Reticulitermes banyulensis, Reticulitermesgrassei, Reticulitermes flavipes (eastern subterranean termite),Reticulitermes hageni, Reticulitermes hesperus (western subterraneantermite), Reticulitermes santonensis, Reticulitermes speratus,Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermesspp., and Zootennopsis spp. (rotten-wood termites).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Lepidoptera (moths and butterflies)including, but not limited to, Achoea janata, Adoxophyes spp.,Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (blackcutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana,Amyelosis transitella (navel orangeworm), Anacamptodes defectaria,Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper),Anticarsia gemmatalis (velvetbean caterpillar), Archips argyrospila(fruittree leafroller), Archips rosana (rose leaf roller), Argyrotaeniaspp. (tortricid moths), Argyrotaenia citrana (orange tortrix),Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder),Bucculatrix thurberiella (cotton leafperforator), Caloptilia spp. (leafminers), Capua reticulana, Carposina niponensis (peach fruit moth),Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneurarosaceana (obliquebanded leafroller), Chrysodeixis spp., Cnaphalocerusmedinalis (grass leafroller), Colias spp., Conpomorpha cramerella,Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydiafunebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maraca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarpa, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth). In at least some embodiments, the methodof the present disclosure may be used to control Spodoptera exigua.

The method of the present disclosure may be used to also control membersof the Order Mallophaga (chewing lice) including, but not limited to,Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken bodylouse), and Menopon gallinea (common hen louse).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Orthoptera (grasshoppers, locusts,and crickets) including, but not limited to, Anabrus simplex (Mormoncricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplusspp. (grasshoppers), Microcentrum retinerve (angularwinged katydid),Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata(forktailed bush katydid), and Valanga nigricorni.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Phthiraptera (sucking lice) including,but not limited to, Haematopinus spp. (cattle and hog lice), Linognathusovillus (sheep louse), Pediculus humanus capitis (human body louse),Pediculus humanus humanus (human body lice), and Pthirus pubis (crablouse).

In particular embodiments, the method of the present disclosure may beused to control members of the Order Siphonaptera (fleas) including, butnot limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis(cat flea), and Pulex irritans (human flea).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Thysanoptera (thrips) including,but not limited to, Frankliniella fusca (tobacco thrips), Frankliniellaoccidentalis (western flower thrips), Frankliniella shultzei,Frankliniella williamsi (corn thrips), Heliothrips haemorrhaidalis(greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp.,Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow teathrips), Taeniothrips rhopalantennalis, and Thrips spp.

The method of the present disclosure may be used to also control membersof the Order Thysanura (bristletails) including, but not limited to,Lepisma spp. (silverfish) and Thermobia spp. (firebrats).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Acari (mites and ticks) including, butnot limited to, Acarapsis woodi (tracheal mite of honeybees), Acarusspp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mangobud mite), Aculops spp., Aculops lycopersici (tomato russet mite),Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rustmite), Amblyomma americanum (lone star tick), Boophilus spp. (ticks),Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and blackflat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks),Dermacentor variabilis (american dog tick), Dermatophagoidespteronyssinus (house dust mite), Eotetranycus spp., Eotetranychuscarpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodesspp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp.,Oligonychus coffee, Oligonychus dims (southern red mite), Panonychusspp., Panonychus citri (citrus red mite), Panonychus ulmi (European redmite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemunlatus (broad mite), Rhipicephalus sanguineus (brown dog tick),Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite),Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae(twospotted spider mite), and Varroa destructor (honey bee mite).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Nematoda (nematodes) including, butnot limited to, Aphelenchoides spp. (foliar nematodes), Belonolaimusspp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilariaimmitis (dog heartworm), Ditylenchus spp. (stem and bulb nematodes),Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode),Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lancenematodes), Meloidogyne spp. (root knot nematodes), Meloidogyneincognita (root knot nematode), Onchocerca volvulus (hook-tail worm),Pratylenchus spp. (lesion nematodes), Radopholus spp. (burrowingnematodes), and Rotylenchus reniformis (kidney-shaped nematode).

In at least some embodiments, the method of the present disclosure maybe used to control at least one insect in one or more of the OrdersLepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera,Orthoptera, Diptera, Hymenoptera, and Siphonaptera, and at least onemite in the Order Acari.

Insecticidal Testing Example A Bioassay for Green Peach Aphid (Myzuspersicae) (GPA) (MYZUPE)

The green peach aphid (Myzus persicae) is the most significant aphidpest of peach trees, causing decreased growth, shriveling of the leaves,and the death of various tissues. It is also hazardous because it actsas a vector for the transport of plant viruses, such as potato virus Yand potato leafroll virus to members of the nightshade/potato familySolanaceae, and various mosaic viruses to many other food crops. GPAattacks such plants as broccoli, burdock, cabbage, carrot, cauliflower,daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers,sweet potatoes, tomatoes, watercress, and zucchini, among other plants.GPA also attacks many ornamental crops such as carnation, chrysanthemum,flowering white cabbage, poinsettia, and roses. GPA has developedresistance to many pesticides.

Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) trueleaves, were used as test substrate. The seedlings were infested with20-50 GPA (wingless adult and nymph stages) one day prior to chemicalapplication. Four pots with individual seedlings were used for eachtreatment. Test compounds (2 mg) were dissolved in 2 mL ofacetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm testcompound. The stock solutions were diluted 5× with 0.025% Tween 20 inH₂O to obtain the solution at 200 ppm test compound. A hand-heldaspirator-type sprayer was used for spraying a solution to both sides ofcabbage leaves until runoff. Reference plants (solvent check) weresprayed with the diluent only containing 20% by volume ofacetone/methanol (1:1) solvent. Treated plants were held in a holdingroom for three days at approximately 25° C. and ambient relativehumidity (RH) prior to grading. Evaluation was conducted by counting thenumber of live aphids per plant under a microscope. Percent control wasmeasured by using Abbott's correction formula (W. S. Abbott, “A Methodof Computing the Effectiveness of an Insecticide” J. Econ. Entomol. 18(1925), pp. 265-267) as follows.

Corrected % Control=100*(X−Y)/X

where

X=No. of live aphids on solvent check plants and

Y=No. of live aphids on treated plants

The results are indicated in the table entitled “TABLE 2. BiologicalData for Green Peach Aphid (GPA) (MYZUPE) and SweetpotatoWhitefly-crawler (WF) (BEMITA)” (See Table Section).

Example B Insecticidal Test for Sweetpotato Whitefly-Crawler (Bemisiatabaci) (WF) (BEMITA) in Foliar Spray Assay

The sweetpotato whitefly (Bemisia tabaci) has been reported as a seriouspest of cultivated crops world-wide. It has an extremely wide host rangeattacking more than 500 species of plants from 63 plant families. Weedsoften serve as alternate hosts of crop pests. Direct feeding damage iscaused by the piercing and sucking sap from the foliage of plants. Thisfeeding causes weakening and early wilting of the plant and reduces theplant growth rate and yield. Indirect damage results by the accumulationof honeydew produced by the whiteflies. Honeydew serves as a substratefor the growth of black sooty mold on leaves and fruit reducingphotosynthesis and lessens the market value of the plant or yield.Damage is also caused when sweetpotato whitefly vectors plant viruses.The sweetpotato whitefly is considered the most common and importantwhitefly vector of plant viruses worldwide.

Cotton plants (Gossypium hirsutum) grown in 3-inch pots, with 1 small(4-5 cm) true leaves, were used as test substrate. The plants wereinfested with 200-400 whitefly eggs 4-5 days prior to chemicalapplication. Four pots with individual plants were used for eachtreatment. Test compounds (2 mg) were dissolved in 1 mL of acetonesolvent, forming stock solutions of 2000 ppm test compound. The stocksolutions were diluted 10× with 0.025% Tween 20 in H₂O (diluents) toobtain the solution at 200 ppm test compound. A hand-held aspirator-typesprayer was used for spraying a solution to both sides of cotton leavesuntil runoff. Reference plants (solvent check) were sprayed with thediluent only containing 10% by volume of acetone solvent. Treated plantswere held in a holding room for 9 days at approximately 25° C. andambient relative humidity (RH) prior to grading. Evaluation wasconducted by counting the number of live 3-4 nymph stage per plant undera microscope. Percent control was measured by using Abbott's correctionformula (W. S. Abbott, “A Method of Computing the Effectiveness of anInsecticide” J. Econ. Entomol. 18 (1925), pp. 265-26′7) as follows.

Corrected % Control=100*(X−Y)/X

where

X=No. of live nymphs on solvent check plants and

Y=No. of live nymphs on treated plants.

The results are indicated in the table entitled “TABLE 2. BiologicalData for Green Peach Aphid (GPA) (MYZUPE) and SweetpotatoWhitefly-crawler (WF) (BEMITA)” (See Table Section). The mortalityefficiency of the disclosed pesticidal compounds against GPA and WFinsects was rated as shown in TABLE 1.

TABLE 1 Mortality Rating for Green Peach Aphid and Whitefly % Control(or Mortality) Rating 80-100 A More than 0-Less than 80 B Not Tested CNo activity noticed in this bioassay D

TABLE 2 Biological Data for GPA (MYZUPE) and WF-crawler (BEMITA) InsectSpecies GPA WF No. 200 ppm 200 ppm F2 A A F3 A A F4 A A F5 A A F6 A A F7A A F8 A A F9 A A C3 A A P1 A A P2 A A P3 A A P4 A A P5 A A P6 C A P7 AA P8 A A P10 A A P16 A A P17 A A P19 A A P22 A A P31 A A P32 A A FA1 A AFA2 A A FA3 A A FA4 A A FA5 A A FA6 A A FA7 A A FA8 A A FA9 A A FA10 A AFA11 A A FA12 A A FA13 A A FA14 A A CA1 B B CA2 B B CA3 D C CA4 C C CA5B B CA6 B D CA7 A A CA8 B A CA9 A A CA10 C C CA11 C C CA12 A A CA13 C CCA14 B B CA15 C C CA16 C C

The following examples serve to explain embodiments of the presentinvention in more detail. These examples should not be construed asbeing exhaustive or exclusive as to the scope of this invention.

EXAMPLES

These examples are for illustration purposes and are not to be construedas limiting the disclosure to only the embodiments disclosed in theseexamples.

Starting materials, reagents, and solvents that were obtained fromcommercial sources were used without further purification. Anhydroussolvents were purchased as SURE/SEAL™ from Aldrich and were used asreceived. Melting points were obtained on a Thomas Hoover Unimeltcapillary melting point apparatus or an OptiMelt Automated Melting PointSystem from Stanford Research Systems and are uncorrected. Examplesusing “room temperature” were conducted in climate controlledlaboratories with temperatures of from about 20° C. to about 24° C.Molecules are given their known names, named according to namingprograms within ISIS Draw, ChemDraw or ACD Name Pro. If such programsare unable to name a molecule, the molecule is named using conventionalnaming rules. ¹H NMR spectral data are in ppm (δ) and were recorded at300, 400 or 600 MHz. ¹³C NMR spectral data are in ppm (δ) and wererecorded at 75, 100 or 150 MHz. ¹⁹F NMR spectral data are in ppm (δ) andwere recorded at 376 MHz, unless otherwise stated.

Example 1 Preparation of N,N-di-tent-butoxycarbonyl(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)amine Compound C1

N-chlorosuccinimide (14.4 g, 108 mmol) was added to a solution ofN,N-di-tert-butoxycarbonyl (2-(pyridin-3-yl)thiazol-5-yl)amine (preparedas described in the PCT Application No. WO 2010/129497A1) (19.0 g, 50.3mmol) in acetonitrile (MeCN, 250 mL) in a round bottom flask equippedwith heating mantle, reflux condenser and nitrogen inlet. The mixturewas heated to about 65° C. for one hour. Then, the mixture was cooled toroom temperature (about 22° C.) and concentrated under reduced pressureto a volume of about 20 mL. The residue was diluted with ethyl acetate(EtOAc) and diethyl ether, washed with saturated aqueous sodiumbicarbonate (NaHCO₃), dried over magnesium sulfate (MgSO₄), and thenconcentrated under reduced pressure to give a brown solid. The solid waspurified on silica gel eluting with hexanes and EtOAc to give the titlecompound (C1) as a yellow-orange solid (12.5 g, 60%). ¹H NMR (400 MHz,Chloroform-d) δ 9.12 (d, J=2.2 Hz, 1H), 8.70 (dd, J=4.8, 1.7 Hz, 1H),8.22 (dt, J=8.0, 2.0 Hz, 1H), 7.43 (dd, J=8.0, 4.8 Hz, 1H), 1.49 (s,18H). ¹³C NMR (101 MHz, CDCl₃) δ 161.56, 151.54, 149.44, 147.04, 137.98,133.05, 129.69, 128.74, 123.76, 84.51, 27.75. ESIMS m/z: 412 ([M−H]⁻).

Example 2 Preparation of tert-butyl(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)carbamate Compound C2

TFA (25 mL) was added to a solution of N,N-di-tert-butoxycarbonyl(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)amine (C1) (10 g, 24.28 mmol) inCH₂Cl₂ (250 mL). After stirring for 15 minutes, the reaction was pouredportion wise into 600 mL of water containing 20 g of sodium carbonate(Na₂CO₃) and stirred vigorously for 10 minutes. The mixture wastransferred to a separatory funnel and the organic layer was separated,dried with sodium sulfate (Na₂SO₄), and concentrated under reducedpressure to give a red solid. The solid was purified on silica geleluting with hexanes and EtOAc to give the title compound (C2) as abeige solid (3.5 g, 46% yield). ¹H NMR (400 MHz, Chloroform-d) δ 9.11(d, J=2.4 Hz, 1H), 8.63 (dd, J=4.8, 1.7 Hz, 1H), 8.15 (dt, J=8.0, 2.0Hz, 1H), 7.79 (s, 1H), 7.36 (dd, J=8.0, 4.8 Hz, 1H), 1.55 (s, 9H). ¹³CNMR (101 MHz, CDCl3) δ 153.99, 152.01, 150.32, 146.49, 132.53, 129.73,129.24, 123.71, 123.14, 83.13, 28.16. ESIMS m/z 310 ([M−H]⁻).

Example 3 Preparation of tert-butyl(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)(prop-2-yn-1-yl)carbamateCompound C3 (Method A)

Sodium hydride (60% oil suspension, 0.404 g, 10.1 mmol) was added to anice cold solution oftert-butyl(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)carbamate (C2) (3.00 g,9.62 mmol) in DMF (5 mL). The resulting brown-yellow mixture was stirredat room temperature for 10 minutes, and 3-bromoprop-1-yne was added(1.37 g, 11.6 mmol). The mixture was stirred at about 0° C. to 5° C. for30 minutes, and the ice bath removed. After stirring for additional fourhours at room temperature, the reaction was quenched with saturatedaqueous ammonium chloride (NH₄Cl) and diluted with EtOAc. The organicphase was separated, and the aqueous phase was extracted with EtOAc(3×50 mL). The combined EtOAc extract was dried over MgSO₄, filtered,and concentrated under reduced pressure to give the title compound (C3)as a brown solid (2.78 g, 78%) having a melting point of about 74° C. to76° C. ¹H NMR (400 MHz, Chloroform-d) δ 9.11 (d, J=2.2 Hz, 1H), 8.69(dd, J=4.8, 1.6 Hz, 1H), 8.21 (dt, J=8.0, 2.0 Hz, 1H), 7.40 (dd, J=8.1,4.9 Hz, 1H), 4.43 (d, J=2.5 Hz, 2H), 2.33 (t, J=2.5 Hz, 1H), 1.47 (s,9H). ESIMS m/z 350.50 ([M+H]⁺).

Example 4 Preparation of4-chloro-N-(prop-2-yn-1-yl)-2-(pyridin-3-yl)thiazol-5-amine, HClCompound C4

To a solution oftert-butyl(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)(prop-2-yn-1-yl)carbamate(C3) (2.00 g, 5.72 mmol) in dry dioxane (2 mL) was added a solution of4M HCl in dioxane (10.0 mL, 40.0 mmol). A drying tube was attached tothe flask, and the mixture stirred at room temperature for 36 hours. Theorange-yellow solid was filtered and washed with diethyl ether (10 mL)followed by hexanes (10 mL), and dried under high vacuum to give thetitle compound (C4) as an orange solid (1.55 g, 90%) having a meltingpoint of more than about 250° C. ¹H NMR (400 MHz, d₆-DMSO) δ 9.11-8.88(m, 1H), 8.62 (dd, J=5.2, 1.5 Hz, 1H), 8.37 (ddd, J=8.1, 2.3, 1.4 Hz,1H), 7.68 (ddd, J=8.1, 5.2, 0.8 Hz, 1H), 4.75 (bs, 3.95 (d, J=2.5 Hz,2H), 3.27 (t, J=2.4 Hz, 1H) (NH not observed). ESIMS m/z: 250.49([M−HCl+H]⁺).

The following molecules were made in accordance with the proceduresdisclosed in Example 4:

4-Chloro-2-(5-fluoropyridin-3-yl)-N-(prop-2-yn-1-yl)thiazol-5-aminehydrochloride (Compound CA1)

Compound CA1 was isolated as a brown solid (0.992 g, 86%): mp 141-154°C.; ¹H NMR (400 MHz, DMSO-d₆) δ 8.82 (t, J=1.6 Hz, 1H), 8.57 (d, J=2.4Hz, 1H), 8.03 (td, J=2.8, 9.8 Hz, 1H), 6.59 (bs, 2H), 3.99 (d, J=2.4 Hz,2H), 3.31 (t, J=2.4 Hz, 1H); ESIMS m/z 268 ([M+H]⁺).

4-Chloro-N-(prop-2-yn-1-yl)-2-(pyrimidin-5-yl)thiazol-5-aminehydrochloride (Compound CA2)

Compound CA2 was isolated as a brown solid (0.997 g, 81%): mp 214-215°C.; ¹H NMR (400 MHz, DMSO-d₆) δ 9.16 (s, 1H), 9.13 (s, 2H), 6.45 (bs,2H), 4.00 (d, J=2.4 Hz, 2H), 3.32 (t, J=2.4 Hz, 1H); ESIMS m/z 251([M+H]⁺).

Example 5 Preparation ofN-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylthio)-N-(prop-2-yn-1-yl)propanamideusing Method 1 Compound F7

To a solution of4-chloro-N-(prop-2-yn-1-yl)-2-(pyridin-3-yl)thiazol-5-amine, HCl (0.120g, 0.419 mmol) (C4) and DMAP (0.102 g, 0.839 mmol) in THF (3 mL) wasadded 3-(methylthio)propanoyl chloride (0.0639 g, 0.461 mmol). Theresulting mixture was stirred at 50° C. for 1 hour and diluted withsaturated aqueous NH₄Cl and EtOAc. The organic phase was separated, andthe aqueous phase extracted with EtOAc (2×50 mL). The combined EtOAcextract was dried over MgSO₄, filtered, and concentrated under reducedpressure to give a brown gum. This gum was purified on silica geleluting with mixtures of CH₂Cl₂ and methanol to give the title compound(F7) as a light brown gum (0.077 g, 52%).

The following molecules were made in accordance with the proceduresdisclosed in Example 5 (Method 1):

N-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-2-methyl-3-(methylthio)-N-(prop-2-yn-1-yl)propanamide(Compound F9)

N-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-2,2-difluoro-N-(prop-2-yn-1-yl)cyclopropanecarboxamide(Compound F5)

N-(4-Chloro-2-(pyridin-3-yl)thiazol-5-yl)-2-(methylthio)-N-(prop-2-yn-1-yl)acetamide(Compound F4)

N-(4-Chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound FA1)

N-(4-Chloro-2-(5-fluoropyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide(Compound FA2)

Example 6 Preparation ofN-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-2-(methylthio)-N-(prop-2-yn-1-yl)propanamideusing Method 2 Compound F6

To a solution of4-chloro-N-(prop-2-yn-1-yl)-2-(pyridin-3-yl)thiazol-5-amine, HCl (C4)(0.100 g, 0.349 mmol), 2-(methylthio)propanoic acid (0.504 g, 0.419mmol) and DMAP (0.850 mg, 0.699 mmol) in DMF (3 mL) was addedN1-((ethylimino)methylene)-N3,N3-dimethylpropane-1,3-diamine, HCl (0.100g, 0.524 mmol). The resulting mixture was stirred at room temperaturefor two hours. The mixture was diluted with saturated aqueous NH₄Cl andEtOAc. The organic phase was separated and the aqueous phase extractedwith EtOAc (2×50 mL). The combined EtOAc extract was dried over MgSO₄,filtered, and concentrated under reduced pressure to give the titlecompound as a light brown gum (0.0970 g, 79%).

The following molecules were made in accordance with the proceduresdisclosed in Example 6 (Method 2):

N-(4-Chloro-2-(pyridin-3-yl)thiazol-5-yl)-4,4,4-trifluoro-3-(methylthio)-N-(prop-2-yn-1-yl)butanamide (Compound F3)

N-(4-Chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)cyclopropanecarboxamide (Compound F2)

N-(4-Chloro-2-(pyridin-3-yl)thiazol-5-yl)-3--(((2,2-difluorocyclopropyl)methyl)thio)-N-(prop-2-yn-1-yl)propanamide(Compound F8)

Example 7 Preparation of tert-butyl(2,4-dichlorothiazol-5-yl)(prop-2-yn-1-yl)carbamate Compound CA3

To a stirred solution of tert-butyl (2,4-dichlorothiazol-5-yl)carbamate(prepared as described in the PCT Application No. WO 2010/129497A1)(8.50 g, 31.6 mmol) in dry DMF (100 mL) was added sodium hydride (NaH,60% in oil, 1.51 g, 34.7 mmol) portion-wise at 0° C. and the mixturestirred for 30 minutes. To the mixture was added propargyl bromide (4.47g, 37.9 mmol), stirred for 5 minutes, warmed to room temperature, andstirred for additional 3 hours. The reaction mixture was quenched withsaturated aqueous NH₄Cl and extracted with EtOAc (3×100 mL). Thecombined organic layer was washed with water (3×100 mL) and brine (1×100mL), dried over anhydrous Na₂SO₄, filtered and concentrated underreduced pressure to give a brown residue. This residue was purified byflash column chromatography using 10-30% EtOAc/hexanes as eluent toafford the title compound as an off-white solid (5.80 g, 59%): ¹H NMR(400 MHz, CDCl₃) δ 4.36 (d, J=2.0 Hz, 2H), 2.32 (t, J=2.4 Hz, 1H), 1.46(s, 9H); IR (KBr) 3304, 2933, 1681, 1539, 1357, 1288, 1219, 1157 cm⁻¹;ESIMS m/z 251 ([M+H]⁺).

The following molecules were made in accordance with the proceduresdisclosed in Example 7:

tert-Butyl (2-bromo-4-methylthiazol-5-yl)(prop-2-yn-1-yl)carbamate(Compound CA4)

Compound CA4 was synthesized from tert-butyl(2-bromo-4-methylthiazol-5-yl)carbamate (prepared as described in thePCT Application No. WO 2010/129497A1) and was isolated as an off-whitesolid (2.6 g, 82%): mp 82-86° C.; ¹H NMR (400 MHz, CDCl₃) δ 4.28 (s,2H), 2.30 (t, J=2.4 Hz, 1H), 2.26 (s, 3H), 1.43 (s, 9H); ESIMS m/z 333([M+H]⁺).

Example 8 Preparation of tert-butyl(2-bromo-4-methylthiazol-5-yl)(but-3-yn-2-yl)carbamate Compound CA5

To a stirred solution of tert-butyl(2-bromo-4-methylthiazol-5-yl)carbamate (0.300 g, 1.02 mmol) in THF (5.0mL) was added but-3-yn-2-ol (0.120 g, 2.04 mmol), triphenylphosphine(0.530 g, 2.04 mmol), and diisopropylazodiimide (DIAD, 0.410 g, 2.04mmol) slowly at 0° C. under argon atmosphere. The reaction mixture wasstirred under argon atmosphere at room temperature for 16 hours. Thereaction mixture was quenched with cold water (50 mL), concentratedunder reduced pressure and extracted with EtOAc (3×50 mL). The combinedorganic layer was washed with brine (2×50 mL). The layer was dried overanhydrous Na₂SO₄, concentrated under reduced pressure, and purified byflash column chromatography to provide the title compound as a darkbrown gum (0.200 g, 58%): ¹H NMR (400 MHz, CDCl₃) δ 5.27-5.25 (m, 1H),2.31 (d, J=2.0 Hz, 1H), 2.23 (s, 3H), 1.40 (s, 9H), 1.34 (d, J=7.2 Hz,3H); IR (KBr) 3302, 3265, 2980, 2931, 1712, 1564, 1477, 1454, 1415 cm⁻¹;ESIMS m/z 345 ([M+H]⁺).

The following compound was made in accordance with the proceduresdisclosed in Example 8:

tert-Butyl (2-bromo-4-methylthiazol-5-yl)(but-2-yn-1-yl)carbamate(Compound CA6)

Compound CA6 was isolated as a brown gum (0.20 g, 58%): ¹H NMR (400 MHz,CDCl₃) δ 4.22 (s, 2H), 2.24 (s, 3H), 1.80 (s, 3H), 1.42 (s, 9H); IR(KBr) 2978, 2922, 2376, 2345, 2225, 1716, 1568, 1541, 1473 cm⁻¹; ESIMSm/z 345 ([M+H]⁺).

Example 9 Preparation of tert-butyl(4-chloro-2-(pyridin-3-371)thiazol-5-yl)(prop-2-yn-1-yl)carbamateCompound C3 (Method B)

To a stirred solution of tert-butyl(2,4-dichlorothiazol-5-yl)(prop-2-yn-1-yl)carbamate (2.00 g, 6.50 mmol)in 1,2-dimethoxyethane/water (4:1 ratio) was added pyridin-3-ylboronicacid (0.958 g, 7.80 mmol) followed by Na₂CO₃ (2.08 g, 19.5 mmol) at roomtemperature under argon atmosphere. The reaction mixture was purged withargon; tetrakis(triphenylphosphine)palladium(0) (Pd(PPh₃)₄, 0.36 g, 0.32mmol) added, and heated at 110° C. for 5 hours. The reaction mixture wascooled at room temperature, diluted with water (50 mL) and was extractedwith EtOAc (3×50 mL). The combined organic layer was washed with brine(2×20 mL), dried over anhydrous Na₂SO₄, and was concentrated underreduced pressure. The crude residue was purified by flash columnchromatography using 10-100% EtOAc/hexanes as eluent to afford the titlecompound as a white solid (1.0 g, 44% yield): mp 69-72° C.; ¹H NMR (400MHz, CDCl₃) δ 9.11 (d, J=2.0 Hz, 1H), 8.69 (dd, J=1.6, 4.8 Hz, 1H), 8.21(td, J=2.0, 8.0 Hz, 1H), 7.40 (ddd, J=0.8, 4.8, 8.0 Hz, 1H), 4.43 (d,J=2.0 Hz, 2H), 2.33 (t, J=2.4 Hz, 1H), 1.47 (s, 9H); ESIMS m/z 350([M+H]⁺).

The following molecules were made in accordance with the proceduresdisclosed in Example 9:

tert-Butyl (4-methyl-2-(pyridin-3-yl)thiazol-5-yl)(prop-2-yn-1-yl)carbamate (Compound CA7)

Compound CA7 was isolated as a brown gum (1.3 g, 50%): ¹H NMR (400 MHz,CDCl₃) δ 9.10 (s, 1H), 8.64 (t, J=1.2 Hz, 1H), 8.26-8.18 (m, 1H), 7.36(q, J=8.0 Hz, 1H), 4.35 (s, 2H), 2.36 (s, 3H), 2.31 (t, J=2.4 Hz, 1H),1.45 (s, 9H); IR (KBr) 1845, 1707, 1589, 1560, 1490, 1475, 1384, 1278cm⁻¹; ESIMS m/z 330 ([M+H]⁺).

tert-Butyl(2-(5-fluoropyridin-3-yl)-4-methylthiazol-5-yl)(prop-2-yn-1-yl)carbamate (Compound CA8)

Compound CA8 was isolated as an off-white solid (1.20 g, 67%): ¹H NMR(400 MHz, CDCl₃) δ 8.89 (s, 1H), 8.49 (d, J=2.4 Hz, 1H), 7.97-7.93 (m,1H), 4.35 (s, 2H), 2.35 (s, 3H), 2.31 (t, J=2.4 Hz, 1H), 1.45 (s, 9H);ESIMS m/z 350 ([M+H]⁺).

tert-Butyl(4-chloro-2-(5-fluoropyridin-3-yl)thiazol-5-yl)(prop-2-yn-1-yl)carbamate (Compound CA9)

Compound CA9 was isolated as a white solid (1.0 g, 42%): mp 81-83° C.;¹H NMR (400 MHz, CDCl₃) δ 8.90 (s, 1H), 8.55 (d, J=2.8 Hz, 1H), 7.97(td, J=2.4, 8.8 Hz, 1H), 4.43 (d, J=2.4 Hz, 2H), 2.34 (t, J=2.4 Hz, 1H),1.47 (s, 9H); ESIMS m/z 368 ([M+H]⁺).

tert-Butyl (4-chloro-2-(pyrimidin-5-yl)thiazol-5-yl)(prop-2-yn-1-yl)carbamate (Compound CA10)

Compound CA10 was isolated as a white solid (1.36 g, 60%): mp 80-83° C.;¹H NMR (400 MHz, CDCl₃) δ 9.28 (s, 1H), 9.22 (s, 2H), 4.44 (d, J=2.4 Hz,2H), 2.34 (t, J=2.4 Hz, 1H), 1.48 (s, 9H); ESIMS m/z 351 ([M+H]⁺).

tert-Butyl but-2-yn-1-yl(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)carbamate(Compound C11)

Compound CA11 was isolated as a brown gum (0.45 g, 56%): ¹H NMR (400MHz, CDCl₃) δ 9.10 (s, 1H), 8.64 (q, J=4.8 Hz, 1H), 8.20-8.17 (m, 1H),7.36 (q, J=8.0 Hz, 1H), 4.30-4.29 (m, 2H), 2.34 (s, 3H), 1.81 (s, 3H),1.44 (s, 9H); IR (KBr) 2978, 2922, 2858, 2306, 2225, 1720, 1699, 1556,1487 cm⁻¹; ESIMS m/z 344 ([M+H]⁺).

tert-Butyl but-3-yn-2-yl(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)carbamate(Compound CA12)

Compound CA12 was isolated as a brown solid (0.08 g, 38%): mp 110-123°C.; ¹H NMR (400 MHz, CDCl₃) δ 9.12 (s, 1H), 8.64 (q, J=4.8 Hz, 1H),8.22-8.19 (m, 1H), 7.36 (q, J=8.0 Hz, 1H), 5.33-5.29 (m, 1H), 2.35 (s,1H), 2.32 (s, 3H), 1.42 (s, 9H), 1.26 (d, J=6.4 Hz, 3H); ESIMS m/z 344([M+H]⁺).

Example 10 Preparation ofN-(but-3-yn-2-yl)-4-methyl-2-(pyridin-3-yl)thiazol-5-amine Compound CA13

To a solution of tert-butylbut-3-yn-2-yl(4-methyl-2-(pyridin-3-yl)thiazol-5-yl) carbamate (0.780 g,2.29 mmol) in CH₂Cl₂ (5.0 mL) was added TFA (5.0 mL) at room temperatureunder nitrogen atmosphere. The reaction mixture was stirred at roomtemperature for 3 hours. The reaction mixture was concentrated underreduced pressure, basified with a NaHCO₃ solution (25 mL), and extractedwith EtOAc (3×25 mL). The combined organic layer was washed with brine(2×50 mL), dried over anhydrous Na₂SO₄, and concentrated under reducedpressure. The crude residue was triturated with hexanes (2×25 mL) andwas dried under vacuum to afford the title compound as a yellow solid(0.55 g, 96%): ESIMS m/z 244 ([M+H]⁺). The crude material was used insubsequent reactions with no further purification.

The following molecules were made in accordance with the proceduresdisclosed in Example 10:

4-Methyl-N-(prop-2-yn-1-yl)-2-(pyridin-3-yl)thiazol-5-amine (CompoundCA14)

Compound CA14 was isolated as a yellow solid (0.85 g, 82%); ESIMS m/z230 ([M+H]⁺). The crude material was used in subsequent reactions withno further purification.

2-(5-Fluoropyridin-3-yl)-4-methyl-N-(prop-2-yn-1-yl)thiazol-5-amine(Compound CA15)

Compound CA15 was isolated as a yellow solid (0.85 g, 99%): ESIMS m/z250 ([M+H]⁺). The crude material was used in subsequent reactions withno further purification.

N-(But-2-yn-1-yl)-4-methyl-2-(pyridin-3-yl)thiazol-5-amine (CompoundCA16)

Compound CA16 was isolated as a brown gum (0.60 g, 93%): ESIMS m/z 244([M+H]⁺). The crude material was used in subsequent reactions with nofurther purification.

Example 11 Preparation ofN-(4-chloro-2-(pyrimidin-5-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamideCompound FA3

To a solution of4-chloro-N-(prop-2-yn-1-yl)-2-(pyrimidin-5-yl)thiazol-5-aminehydrochloride (0.463 g, 1.85 mmol) and DMAP (0.563 g, 4.62 mmol) in1,2-dichloroethane (15 mL) was added3-((3,3,3-trifluoropropyl)thio)propanoyl chloride (0.814 g, 3.70 mmol).The resulting mixture was stirred at room temperature for 16 hours anddiluted with EtOAc. The mixture was washed with saturated aqueous NaHCO₃and brine, dried over MgSO₄, filtered, and concentrated under reducedpressure to give a brown gum. This gum was purified by flash columnchromatography using EtOAc/hexanes as eluent to provide the titlecompound as a brown solid (0.225 g, 28%).

The following molecules were made in accordance with the proceduresdisclosed in Example 11:

N-(4-Methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylthio)-N-(prop-2-yn-1-yl)propanamide(Compound P1)

2-Methyl-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylthio)-N-(prop-2-yn-1-yl)propanamide (Compound P2)

N-(4-Methyl-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound P6)

3-(((2,2-Difluorocyclopropyl)methyl)thio)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)propanamide(Compound P10)

N-(2-(5-Fluoropyridin-3-yl)-4-methylthiazol-5-yl)-3-(methylthio)-N-(prop-2-yn-1-yl)propanamide(Compound FA4)

N-(2-(5-Fluoropyridin-3-yl)-4-methylthiazol-5-yl)-2-methyl-3-(methylthio)-N-(prop-2-yn-1-yl)propanamide (Compound FA5)

N-(2-(5-Fluoropyridin-3-yl)-4-methylthiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide(Compound P19)

3-(((2,2-Difluorocyclopropyl)methyl)thio)-N-(2-(5-fluoropyridin-3-yl)-4-methylthiazol-5-yl)-N-(prop-2-yn-1-yl)propanamide(Compound P22)

N-(But-2-yn-1-yl)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound P16)

N-(But-2-yn-1-yl)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylthio)propanamide(Compound P17)

N-(But-2-yn-1-yl)-3-(((2,2-difluorocyclopropyl)methyl)thio)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)propanamide(Compound FA14)

N-(But-3-yn-2-yl)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound P32)

N-(But-3-yn-2-yl)-3-(((2,2-difluorocyclopropyl)methyl)thio)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)propanamide(Compound P31)

Example 12 Preparation ofN-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3trifluoropropyl)sulfinyl)propanamideCompound FA6

To a solution ofN-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-(3,3,3-trifluoropropyl)thio)propanamide(0.20 g, 0.46 mmol) in acetic acid (AcOH. 2.0 mL) was added sodiumperborate tetrahydrate (0.060 g, 0.46 mmol) at room temperature and wasstirred for 3 hours. The reaction mixture was diluted with EtOAc (100mL), washed with water (10 mL), saturated aqueous NaHCO₃ (2×20 mL) andbrine (2×20 mL). The separated organic layer was dried over anhydrousNa₂SO₄ and concentrated under reduced pressure. The crude residue waspurified by flash column chromatography using 1-5% MeOH/CH₂Cl₂) toprovide the title compound as a brown gum (0.074 mg, 36%).

The following molecules were made in accordance with the proceduresdisclosed in Example 12:

N-(4-Chloro-2-(5-fluoropyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(Compound FA7)

N-(4-Chloro-2-(pyrimidin-5-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(Compound FA8)

N-(4-Methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylsulfinyl)-N-(prop-2-yn-1-yl)propanamide(Compound P3)

2-Methyl-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylsulfinyl)-N-(prop-2-yn-1-yl)propanamide (Compound P5)

N-(4-Methyl-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (Compound P7)

3-(((2,2-Difluorocyclopropyl)methyl)sulfinyl)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)propanamide(Compound FA9)

Example 13 Preparation ofN-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfonyl)propanamideCompound FA10

To a stirred solution ofN-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide(0.187 g, 0.430 mmol) in AcOH (2.0 mL) was added sodium perboratetetrahydrate (0.139 g, 1.07 mmol) at room temperature and was stirred at60° C. for 3 hours. The reaction mixture was diluted with EtOAc (100mL), washed with water (1×10 mL), saturated aqueous NaHCO₃ (2×20 mL) andbrine (1×20 mL). The separated organic layer was dried over anhydrousNa₂SO₄ and concentrated under reduced pressure. The crude residue waspurified by flash column chromatography using 10-50% EtOAc/hexanes aseluent to provide the title compound as a light brown solid (0.0520 g,23%).

The following molecules were made in accordance with the proceduresdisclosed in Example 13:

N-(4-Chloro-2-(5-fluoropyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfonyl)propanamide(Compound FA11)

N-(4-Chloro-2-(pyrimidin-5-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfonyl)propanamide (Compound FA12)

N-(4-Methyl-2-(pyridin-3-yl)thiazol-5-yl)-3-(methylsulfonyl)-N-(prop-2-yn-1-yl)propanamide(Compound P4)

N-(4-Methyl-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfonyl)propanamide (Compound P8)

3-(((2,2-Difluorocyclopropyl)methyl)sulfonyl)-N-(4-methyl-2-(pyridin-3-yl)thiazol-5-yl)-N-(prop-2-yn-1-yl)propanamide(Compound FA13)

TABLE 3 shows non-limiting examples of the compound of formula I.Compounds F2, F3, F6, and F8 were prepared according to Example 6.Compounds F4, F5, F7, F9, FA1, and FA2 were prepared according toExample 5. Compounds FA3, FA4, FA5, FA14, P1, P2, P6, P10, P19, P22,P16, P17, P32, and P31 were prepared according to Example 11. CompoundsFA6, FA7, FA8, FA9, P3, P5, and P7 were prepared according to Example12. Compounds FA10, FA11, FA12, FA13, P4, and P8 were prepared accordingto Example 13.

TABLE 3 No. Structure ESIMS (m/z) ¹H NMR (400 MHz, Chloroform-d), IR, mpF2

Brown Gum 318 ([M + H]⁺) δ 9.23-9.10 (m, 1H), 8.72 (dd, J = 4.8, 1.6 Hz,1H), 8.24 (ddd, J = 7.9, 2.3, 1.6 Hz, 1H), 7.43 (ddd, J = 8.0, 4.9, 0.8Hz, 1H), 4.21 (m, 2H), 4.01 (dd, J = 6.3, 2.5 Hz, 1H), 2.32 (t, J = 2.5Hz, 1H), 1.12 (m, 2H), 0.83 m, 2H) F3

Brown Oil 420 ([M + H]⁺) δ 9.15 (dd, J = 2.5, 0.9 Hz, 1H), 8.74 (dd, J =4.8, 1.6 Hz, 1H), 8.30-8.17 (m, 1H), 7.44 (ddd, J = 8.0, 4.8, 0.8 Hz,1H), 4.95 (m, 1H), 4.18 (m, 1H), 3.73 (q, J = 10.1, 9.3 Hz, 1H), 2.70(m, 1H,), 2.53 (m, 1H), 2.35 (t, J = 2.5 Hz 1H), 2.29(s, 3H) IR (thinfilm) 3291, 2927, 1684 cm⁻¹ F4

Brown Solid 338 ([M + H]⁺) δ 9.14 (dd, J = 2.3, 0.8 Hz, 1H), 8.73 (dd, J= 4.8, 1.6 Hz, 1H), 8.23 (ddd, J = 8.0, 2.3, 1.6 Hz, 1H), 7.43 (ddd, J =8.0, 4.8, 0.9 Hz, 1H), 4.96 (s, 1H), 4.12 (s, 1H), 3.21 (s, 2H), 2.34(t, J = 2.5 Hz, 1H), 2.22 (s, 3H) F5

Brown Gum 354 ([M + H]⁺) δ 9.16 (d, J = 2.3 Hz, 1H), 8.74 (dd, J = 4.8,1.6 Hz, 1H), 8.25 (dt, J = 8.1, 1.9 Hz, 1H), 7.45 (ddd, J = 8.0, 4.8,0.8 Hz, 1H), 4.21 (m, 1H), 4.01 (dd, J = 6.0, 2.5 Hz, 1H), 2.39-2.32 (m,2H), 2.27 (dt, J = 12.5, 6.8 Hz, 1H), 1.77-1.65 (m, 1H) IR (thin film)3271, 3210, 3034, 1694 cm⁻¹ F6

Light Brown Oil 352 ([M + H]⁺) δ 9.14 (d, J = 2.2 Hz, 1H), 8.72 (dd, J =4.8, 1.6 Hz, 1H), 8.23 (ddd, J = 8.0, 2.3, 1.6 Hz, 1H), 7.43 (ddd, J =8.0, 4.8, 0.9 Hz, 1H), 4.94 (d, J = 17.1 Hz, 1H), 4.12 (q, J = 7.1 Hz,1H), 2.80 (m, 1H), 2.33 (s, 1H), 2.09 (s, 3H), 1.49 (d, J = 6.8 Hz, 3H)IR (thin film) 3256, 2973, 1675 cm⁻¹ F7

Brown Oil 352 ([M + H]⁺) δ 9.14 (dd, J = 2.3, 0.8 Hz, 1H), 8.74 (dd, J =4.8, 1.6 Hz, 1H), 8.24 (dt, J = 8.0, 2.0 Hz, 1H), 7.44 (ddd, J = 8.0,4.8, 0.9 Hz, 1H), 4.20 (bs, 1H), 3.95 (bs, 1H), 2.81 (t, J = 7.2 Hz,2H), 2.56 (m, 2H), 2.33 (s, 1H), 2.08 (s, 3H) IR (thin film) 3254, 2914,1680 cm⁻¹ F8

Brown Gum 428 ([M + H]⁺) δ 9.14 (dd, J = 2.4, 0.8 Hz, 1H), 8.74 (dd, J =4.8, 1.7 Hz, 1H), 8.24 (dt, J = 8.0, 1.9 Hz, 1H), 7.44 (ddd, J = 8.0,4.9, 0.9 Hz, 1H), 4.94 (s, 1H), 4.12 (s, 1H), 2.89 (t, J = 7.2 Hz, 2H),2.70-2.53 (m, 4H), 2.33 (t, J = 2.5 Hz, 1H), 1.76 (td, J = 13.0, 12.3,6.9 Hz, 1H), 1.49 (tdd, J = 12.1, 8.0, 4.7 Hz, 1H), 1.12-0.99 (m, 1H) IR(thin film) 3298, 2922, 1681IR cm⁻¹ F9

Brown Oil 366 ([M + H]⁺) IR (thin film) 3254, 2914, 1680 cm⁻¹ P1

Orange gum 332 ([M + H]⁺) δ 9.19 (s, 1H), 8.73 (s, 1H), 8.36 (d, J = 8.0Hz, 1H), 7.55 (q, J = 8.0 Hz, 1H), 4.57-4.42 (m, 2H), 2.79 (t, J = 7.2Hz, 2H), 2.61? 2.50 (m, 2H), 2.41 (s, 3H), 2.29 (t, J = 2.4 Hz, 1H),2.07 (s, 3H) IR (KBr) 2956, 2926, 2854, 2376, 2345, 2312, 1734, 1685,1375 cm⁻¹ P2

Brown gum 346 ([M + H]+) δ 9.13 (s, 1H), 8.69-8.67 (m, 1H), 8.22-8.20(m, 1H), 7.40 (q, J = 7.6 Hz, 1H), 4.72-4.28 (m, 2H), 2.94- 2.83 (m,2H), 2.47-2.42 (m, 4H), 2.28 (s, 1H), 2.02 (d, J = 8.0 Hz, 3H), 1.18 (s,3H) IR (KBr) 3419, 3255, 2970, 2920, 2852, 2119, 1678, 1598, 1570 cm⁻¹P3

Yellow gum 347 ([M + H]⁺) δ 9.12 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.22-8.19 (m, 1H), 7.40 (q, J = 8.0 Hz, 1H), 4.56-4.43 (m, 2H),3.17-3.10 (m, 1H), 2.92-2.86 (m, 1H), 2.73-2.72 (m, 2H), 2.58 (s, 3H),2.42 (s, 3H), 2.31 (t, J = 2.4 Hz, 1H) IR (KBr) 3203, 3003, 2954, 2920,2852, 2366, 1734, 1716, 1354 cm⁻¹ P4

Brown gum 364 ([M + H]⁺) δ 9.12 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.22-8.19 (m, 1H), 7.40 (q, J = 8.0 Hz, 1H), 4.56-4.41 (m, 2H),3.52-3.41 (m, 2H), 2.96 (s, 3H), 2.76 (t, J = 6.8 Hz, 2H), 2.43 (s, 3H),2.32 (t, J = 2.4 Hz, 1H) IR (KBr) 3431, 3261, 2960, 2922, 2850, 2119,1732, 1683, 1552 cm⁻¹ P5

Brown gum 378 ([M + H]⁺) δ 9.15 (s, 1H), 8.68 (q, J = 4.8 Hz, 1H),8.24-8.20 (m, 1H), 7.38 (q, J = 8.0 Hz, 1H), 4.70-4.27 (m, 2H),3.83-3.77 (m, 1H), 3.33-3.29 (m, 1H), 2.92 (s, 3H), 2.91 (s, 1H), 2.48(d, J = 12.0 Hz, 3H), 2.31 (t, J = 2.4 Hz, 1H), 1.25 (s, 3H) IR (KBr)2924, 2852, 2351, 2310, 1681, 1633, 1591, 1552, 1435 cm⁻¹ P6

Brown gum 414 ([M + H]⁺) δ 9.26 (s, 1H), 8.78 (s, 1H), 8.54 (d, J = 8.0Hz, 1H), 7.73 (q, J = 8.0 Hz, 1H), 4.70-4.65 (m, 2H), 2.85 (t, J = 6.8Hz, 2H), 2.66 (t, J = 8.1 Hz, 2H), 2.48-2.39 (m, 2H), 2.38 (s, 3H),2.37-2.33 (m, 3H) IR (KBr) 2927, 2378, 2345, 2310, 1716, 1683, 1558,1508, 1386 cm⁻¹ P7

Yellow gum 429 ([M + H]⁺) δ 9.12 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.22-8.19 (m, 1H), 7.40 (q, J = 8.0 Hz, 1H), 4.45-4.42 (m, 2H),3.19-3.12 (m, 1H), 2.96-2.85 (m, 3H), 2.75-2.74 (m, 2H), 2.66-2.57 (m,2H), 2.42 (s, 3H), 2.31 (t, J = 2.4 Hz, 1H) IR (KBr) 3313, 3226, 2926,2854, 2349, 2115, 1668, 1589, 1394 cm⁻¹ P8

Off-white solid 446 ([M + H]⁺) δ 9.12 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.22-8.19 (m, 1H), 7.40 (q, J = 8.0 Hz, 1H), 4.57-4.30 (m, 2H),3.44-3.42 (m, 2H), 3.28 (s, 3H), 2.76 (t, J = 6.8 Hz, 2H), 2.43 (s, 3H),2.37 (s, 1H), 2.31 (t, J = 2.4 Hz, 1H) mp 117-120° C. P10

Brown gum 408 ([M + H]⁺) δ 9.27 (s, 1H), 8.79 (s, 1H), 8.57 (d, J = 8.0Hz, 1H), 7.76 (q, J = 8.0 Hz, 1H), 4.62-4.50 (m, 2H), 2.87 (t, 6.8 Hz,2H), 2.60 (t, J = 7.6 Hz, 2H), J = 2.49 (t, J = 6.8 Hz, 2H), 2.42 (s,3H), 2.30 (s, 1H), 1.80-1.69 (m, 1H), 1.52-1.42 (m, 1H), 1.08-1.00 (m,1H) IR (KBr) 2927, 2378, 2345, 1734, 1716, 1683, 1653, 1647, 1558 cm⁻¹P16

Yellow gum 428 ([M + H]⁺) δ 9.05 (s, 1H), 8.60 (q, J = 4.8 Hz, 1H),8.15-8.13 (m, 1H), 7.33 (q, J = 8.0 Hz, 1H), 4.45-4.27 (m, 2H), 2.77 (t,J = 7.2 Hz, 2H), 2.59 (t, J = 8.4 Hz, 2H), 2.44-2.33 (m, 2H), 2.32 (s,3H), 2.31-2.23 (m, 2H), 1.72 (t, J = 4.4 Hz, 3H) IR (KBr) 2922, 1681,1558, 1506, 1489, 1456, 1419, 1309 cm⁻¹ P17

Yellow gum 346 ([M + H]⁺) δ 9.06 (s, 1H), 8.60 (q, J = 4.8 Hz, 1H),8.15-8.12 (m, 1H), 7.33 (q, J = 8.0 Hz, 1H), 4.45-4.27 (m, 2H), 2.72 (t,J = 7.2 Hz, 2H), 2.51-2.37 (m, 2H), 2.32 (s, 3H), 1.99 (s, 3H), 1.72 (t,J = 4.4 Hz, 3H) IR (KBr) 2958, 2920, 2852, 2378, 2306, 1734, 1716, 1683,1473 cm⁻¹ P19

Yellow gum 432 ([M + H]⁺) δ 8.91 (s, 1H), 8.54 (s, 1H), 7.96 (d, J = 8.8Hz, 1H), 4.56-4.42 (m, 2H), 2.84 (t, J = 6.8 Hz, 2H), 2.66 (t, J = 7.6Hz, 2H), 2.49-2.47 (m, 2H), 2.40 (s, 3H), 2.38-2.30 (s, 3H) IR (KBr)2962, 2345, 1683, 2924, 2852, 2347, 1749, 1683, 1473 cm⁻¹ P22

Yellow gum 425 ([M + H]⁺) δ 8.84 (s, 1H), 8.47 (s, 1H), 7.92 (d, J = 8.8Hz, 1H), 4.50-4.35 (m, 2H), 2.80 (t, J = 8.0 Hz, 2H), 2.55-2.51 (m, 2H),2.44-2.34 (m, 2H), 2.33 (s, 3H), 2.22 (t, J = 2.4 Hz, 1H), 1.73- 1.62(m, 1H), 1.45-1.34 (m, 1H), 1.01-0.96 (m, 1H) IR (KBr) 2962, 2345, 1693,1683, 12845, 1261, 1138, 1099, 1020 cm⁻¹ P31

Yellow gum 422 ([M + H]⁺) δ 9.10 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.27-8.25 (m, 1H), 7.54 (q, J = 8.0 Hz, 1H), 5.54-5.57 (m, 1H),3.21-3.17 (m, 1H), 2.78 (t, J = 7.2 Hz, 2H), 2.67 (t, J = 1.6 Hz, 2H),2.62-2.55 (m, 2H), 2.47-2.35 (m, 2H), 2.29 (s, 1H), 1.84-1.69 (m, 1H),1.59-1.53 (m, 1H), 1.37-1.36 (m, 3H), 1.19-1.15 (m, 1H) IR (KBr) 2927,2854, 2360, 2341, 1676, 1550, 1442, 1371, 1307 cm⁻¹ P32

Yellow gum 428 ([M + H]⁺) (400 MHz, DMSO-d₆) δ 9.10 (s, 1H), 8.69 (q, J= 4.8 Hz, 1H), 8.27-8.25 (m, 1H), 7.54 (q, J = 8.0 Hz, 1H), 5.59-5.55(m, 1H), 3.17 (s, 1H), 2.80 (t,J = 6.8 Hz, 1H), 2.66 (t, J = 6.8 Hz,1H), 2.46-2.45 (m, 5H), 2.35 (s, 3H), 2.29 (s, 1H), 1.36 (d, J = 4.8 Hz,3H) IR (KBr) 3439, 3304, 2926, 2854, 2360, 2331, 1676, 1551, 1469 cm⁻¹FA1

Brown solid 434 ([M + H]⁺) δ 9.14 (d, J = 2.0 Hz, 1H), 8.74 (dd, J =1.2, 4.8 Hz, 1H), 8.24 (td, J = 2.0, 8.0 Hz, 1H), 7.44 (dd, J = 4.8, 8.0Hz, 1H), 4.93 (bs, 1H), 4.13 (bs, 1H), 2.86 (t, J = 7.2 Hz, 2H),2.70-2.65 (m, 2H), 2.55 (bs, 2H), 2.43-2.31 (m, 3H) IR (KBr) 3304, 2931,1685, 1525, 1371, 1274, 1242 cm⁻¹ FA2

Brown solid 462 ([M + H]⁺) δ 8.93 (s, 1H), 8.60 (d, J = 2.4 Hz, 1H),8.00 (td, J = 2.4, 8.8 Hz, 1H), 4.95 (bs, 1H), 4.13 (bs, 1H), 2.86 (t, J= 7.2 Hz, 2H), 2.70-2.66 (m, 2H), 2.54 (bs, 2H), 2.43-2.34 (m, 3H) mp117-119° C. FA3

Brown solid 435 ([M + H]⁺) δ 9.33 (s, 1H), 9.25 (s, 2H), 4.95 (bs, 1H),4.13 (bs, 1H), 2.87 (t, J = 7.2 Hz, 2H), 2.70-2.66 (m, 2H), 2.54 (s,2H), 2.43-2.31 (m, 3H) mp 102-103° C. FA4

Brown gum 349 ([M + H]⁺) δ 8.91 (s, 1H), 8.54 (s, 1H), 7.96 (d, J = 8.8Hz, 1H), 4.56-4.25 (m, 2H), 2.79 (t, J = 7.2 Hz, 2H), 2.49 (t, J = 6.0Hz, 2H), 2.41 (s, 3H), 2.29 (d, 2.4 Hz, 1H), 2.06 (s, 3H) IR (KBr) 3064,2962, 2349, 2310, 1683, 1558, 1548, 1448, 1261 cm⁻¹ FA5

Yellow gum 363 ([M + H]⁺) δ 8.92 (s, 1H), 8.54 (s, 1H), 7.97 (d, J = 8.8Hz, 1H), 4.74-4.27 (m, 2H), 2.92-2.83 (m, 2H), 2.47-2.42 (m, 4H), 2.29(t, J = 2.0 Hz, 1H), 2.03 (s, 3H), 1.18 (s, 3H) IR (KBr) 3255, 3049,2972, 2349, 1681, 1598, 1550, 1506, 1301 cm⁻¹ FA6

Brown gum 450 ([M + H]⁺) δ 9.14 (d, J = 1.6 Hz, 1H), 8.74 (dd, J = 1.6,4.8 Hz, 1H), 8.23 (td, J = 2.0, 8.0 Hz, 1H), 7.44 (dd, J = 4.8, 8.0 Hz,1H), 4.91 (bs, 1H), 4.14 (bs, 1H), 3.17 (bs, 1H), 3.01-2.85 (m, 3H),2.80 (t, J = 6.8 Hz, 2H), 2.67-2.55 (m, 2H), 2.35 (t, J = 2.4 Hz, 1H) IR(KBr) 2370, 2345, 1685, 1523, 1421, 1271, 1138 cm⁻¹ FA7

Brown gum 468 ([M + H]⁺) δ 8.93 (s, 1H), 8.61 (s, 1H), 7.99 (d, J = 8.8Hz, 1H), 4.94 (bs, 1H), 4.15 (bs, 1H), 3.18 (bs, 1H), 2.99-2.85 (m, 3H),2.80 (t, J = 6.4 Hz, 2H), 2.67-2.55 (m, 2H), 2.36 (s, 1H) IR (KBr) 3230,2926, 1683, 1525, 1429, 1338, 1217 cm⁻¹ FA8

Light brown solid 451 ([M + H]⁺) δ 9.33 (s, 1H), 9.24 (s, 2H), 4.62 (bs,1H), 4.16 (bs, 1H), 3.17 (bs, 1H), 2.99-2.83 (m, 3H), 2.79 (t, J = 6.8Hz, 2H), 2.67-2.55 (m, 2H), 2.36 (s, 1H) mp 129-131° C. FA9

Yellow gum 423 ([M + H]⁺) δ 9.11 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.21-8.19 (m, 1H), 7.41 (q, J = 8.0 Hz, 1H), 4.54-4.43 (m, 2H),3.19-3.11 (m, 1H), 2.98-2.73 (m, 5H), 2.42 (s, 3H), 2.31 (t, J = 2.4 Hz,1H), 2.07-1.94 (m, 1H), 1.1H) 71-1.66 (m, 1H), 1.34-1.28 (m, IR (KBr)3226, 2924, 2854, 2349, 2117, 1674, 1589, 1404, 1386 cm⁻¹ FA10

Light brown solid 466 ([M + H]⁺) δ 9.14 (d, J = 2.0 Hz, 1H), 8.75 (dd, J= 1.2 Hz, 4.8 Hz, 1H), 8.24 (td, J = 2.0 Hz, 8.0 Hz, 1H), 7.45 (dd, J =4.8 Hz, 8.0 Hz, 1H), 4.91 (bs, 1H), 4.13 (bs, 1H), 3.51-3.40 (m, 2H),3.28- 3.24 (m, 2H), 2.85 (t, J = 6.8 Hz, 2H), 2.75-2.64 (m, 2H), 2.36(t, J = 2.0 Hz, 1H) mp 123-127° C. FA11

Light brown solid 484 ([M + H]⁺) δ 8.94 (s, 1H), 8.61 (s. 1H), 8.00 (td,J = 2.4 Hz, 8.8 Hz, 1H), 4.93 (bs, 1H), 4.13 (bs, 1H), 3.47 (bs, 2H),3.28-3.24 (m, 2H), 2.84 (t, J = 6.8 Hz, 2H), 2.75-2.64 (m, 2H), 2.37 (t,J = 2.0 Hz, 1H) mp 116-118° C. FA12

Light brown solid 467 ([M + H]⁺) δ 9.34 (s, 1H), 9.25 (s, 2H), 4.94 (bs,1H), 4.13 (bs, 1H), 3.45 (bs, 2H), 3.28-3.24 (m, 2H), 2.83 (t, J = 6.8Hz, 2H), 2.75-2.64 (m, 2H), 2.37 (s, 1H) mp 163-170° C. FA13

Brown gum 440 ([M + H]⁺) δ 9.13 (s, 1H), 8.69 (q, J = 4.8 Hz, 1H),8.24-8.22 (m, 1H), 7.42 (q, J = 8.0 Hz, 1H), 4.56-4.41 (m, 2H),3.43-3.41 (m, 2H), 3.32-3.26 (m, 1H), 3.08-3.03 (m, 1H), 2.78-2.77 (m,2H), 2.43 (s, 3H), 2.32 (t, J = 2.4 Hz, 1H), 2.07-1.98 (m, 1H), 1.77-1.68 (m, 1H), 1.47-1.41 (m, 1H) IR (KBr) 3402, 3282, 3263, 3188, 3053,2964, 2920, 1681, 1589, 1388 cm⁻¹ FA14

Yellow gum 422 ([M + H]⁺) δ 9.12 (s, 1H), 8.68 (q, J = 4.8 Hz, 1H),8.22-8.19 (m, 1H), 7.40 (q, J = 8.0 Hz, 1H), 4.42-4.38 (m, 2H), 2.86 (t,J = 7.2 Hz, 2H), 2.64-2.48 (m, 4H), 2.39 (s, 3H), 1.80 (t, J = 4.4 Hz,3H), 1.79-1.71 (m, 1H), 1.54- 1.43 (m, 1H), 1.07-1.02 (m, 1H) IR (KBr)2956, 2922, 2854, 2376, 2310, 2233, 1680, 1554, 1471 cm⁻¹

TABLE 4 shows further non-limiting examples of the compound of formulaI.

TABLE 4 No. Structure Appearance Prepared according to Example C1

Yellow-Orange Solid 1 C2

Beige Solid 2 C3

Brown Solid 3 C4

Orange Solid 4 CA1

Brown solid 4 CA2

Brown solid 4 CA3

Off-white solid 7 CA4

Off-white solid 7 CA5

Dark brown gum 8 CA6

Brown gum 8 CA7

Brown gum 9 CA8

Off-white solid 9 CA9

White solid 9 CA10

White solid 9 CA11

Brown gum 9 CA12

Brown solid 9 CA13

Yellow solid 10 CA14

Yellow solid 10 CA15

Yellow solid 10 CA16

Brown gum 10

TABLE 5 shows further non-limiting examples of the compound of formulaI.

TABLE 5 May be Prepared according to Example or No. Structure Scheme: P1

Example 6 P2

Example 6 P3

Scheme 3 P4

Scheme 3 P5

Scheme 3 P6

Example 6 P7

Scheme 3 P8

Scheme 3 P9

Example 6 P10

Example 6 P11

Example 6 P12

Example 6 P13

Scheme 3 P14

Scheme 3 P15

Scheme 3 P16

Example 6 P17

Example 6 P18

Example 6 P19

Example 6 P20

Example 6 P21

Example 6 P22

Example 6 P23

Example 6 P24

Example 6 P25

Example 6 P26

Scheme 3 P27

Example 6 P28

Example 6 P29

Example 6 P30

Example 6 P31

Example 6 P32

Example 6 P33

Example 6 P34

Scheme 3

While this invention has been described in certain embodiments, thepresent invention can be further modified within the spirit and scope ofthis disclosure. This application is therefore intended to cover anyvariations, uses, or adaptations of the invention using its generalprinciples. Further, this application is intended to cover suchdepartures from the present disclosure as come within known or customarypractice in the art to which this invention pertains and which fallwithin the limits of the appended claims

We claim:
 1. A pesticidal composition, comprising a compound of formulaI or any agriculturally acceptable salt thereof:

wherein: (a) R₁, R₂, and R₄ are independently hydrogen, F, Cl, Br, I,substituted or unsubstituted C₁-C₆ alkyl, or substituted orunsubstituted C₁-C₆ haloalkyl or substituted or unsubstituted C₁-C1₀cycloalkyl, substituted or unsubstituted C1-C10 halocycloalkyl, whereineach said R₁, R₂, and R₄, when substituted, has one or more substituentsselected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₁-C₆ haloalkyl, C₃-C₁₀ cycloalkyl, or C₃-C₁₀ halocycloalkyl,each of which may be substituted and may optionally be substituted withR₁₀; (b) R₃ is hydrogen, F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₂-C₆ alkynyl, substituted or unsubstitutedC₁-C₆ alkoxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₁-C₆ haloalkyl, substituted orunsubstituted C₆-C₂₀ aryl, substituted or unsubstituted C₁-C₂₀heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀, C(═X₁)N(R₁₀)₂, N(R₁₀)₂,N(R₁₀)C(═X₁)R₁₀, S(O)_(n)R₁₀, S(O)_(n)OR₁₀, or R₁₀S(O)_(n)R₁₀, whereineach said R₃, when substituted, has one or more substituents selectedfrom F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl,C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, each of which is unsubstituted, substituted, orsubstituted with R₁₀; (c) R₅ is selected from hydrogen, F, Cl, Br, I,CN, NO₂, substituted or unsubstituted C₁-C₆ alkyl, substituted orunsubstituted C₂-C₆ alkenyl, substituted or unsubstituted C₁-C₆ alkoxy,C₃-C₁₀ cycloalkyl, substituted or unsubstituted C₆-C₂₀ aryl, substitutedor unsubstituted C₁-C₂₀ heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀,C(═X₁)N(R₁₀)₂, N(R₁₀)₂, N(R₁₀)C(═X₁)R₁₀, SR₁₀, S(O)_(n)OR₁₀, orR₁₀S(O)_(n)R₁₀, wherein each said R₅, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀aryl, or C₁-C₂₀ heterocyclyl, each of which is unsubstituted,substituted, or substituted with R₁₀; (d) Y is a bond or is substitutedor unsubstituted C₁-C₆ alkyl, or substituted or unsubstituted C₂-C₆alkenyl, except where Y is a bond, wherein each Y, when substituted, hasone or more substituents selected from hydrogen, F, Cl, Br, I, CN, NO₂,C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆haloalkyloxy, or C₃-C₁₀ cycloalkyl, optionally Y and R₇ may be connectedin a cyclic arrangement, where optionally such arrangement may have oneor more heteroatoms selected from O, S, or N, in the cyclic structureconnecting Y and R₇; (e) R₆ is selected from hydrogen, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₂-C₆ alkynyl, substituted or unsubstitutedC₃-C₁₀ cycloalkyl, substituted or unsubstituted C₆-C₂₀ aryl, substitutedor unsubstituted C₁-C₂₀ heterocyclyl, C₁-C₆ alkyl-(C₃-C₁₀cyclohaloalkyl) wherein the alkyl and cyclohaloalkyl is independentlysubstituted or unsubstituted, or C₁-C₆ alkyl-(C₃-C₁₀ cycloalkyl),wherein the alkyl and cycloalkyl is independently substituted orunsubstituted, wherein each R₆, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₂-C₆ haloalkenyl,C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OR₁₀,S(O)_(n)OR₁₀, C₆-C₂₀ aryl, C₁-C₂₀ heterocyclyl, or R₁₀ aryl, each ofwhich is unsubstituted, substituted, or substituted with R₁₀; (f) R₇ isR₉, R₈S(O)_(n)R₉; (g) R₈ is substituted or unsubstituted C₁-C₁₂ alkenyl,or C₁-C₁₂ alkynyl, substituted or unsubstituted C₁-C₁₂ alkyl, orsubstituted or unsubstituted C₃-C₁₀ cycloalkyl, wherein each said R₈,when substituted, has one or more substituents selected from F, Cl, Br,I, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₃-C₁₀ cycloalkyl,C₃-C₁₀ halocycloalkyl, OR₁₀, S(O)_(n)R₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, each of which is unsubstituted, substituted, orsubstituted with R₁₀; (h) R₉ is selected from hydrogen, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₁-C₆ alkoxy, substituted or unsubstitutedC₃-C₁₀ cycloalkyl, substituted or unsubstituted C₃-C₁₀ halocycloalkylsubstituted, or unsubstituted C₃-C₁₀ cycloalkenyl, substituted orunsubstituted C₁-C₆ haloalkyl substituted or unsubstituted C₆-C₂₀ aryl,or substituted or unsubstituted C₁-C₂₀ heterocyclyl, wherein each saidR₉, when substituted, has one or more substituents selected from F, Cl,Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₁-C₆ haloalkyloxy,C₂-C₆ haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀halocycloalkyl, C₃-C₁₀ halocycloalkenyl, oxo, OR₁₀, S(O)_(n)R₁₀, C₆-C₂₀aryl, or C₁-C₂₀ heterocyclyl, each of which is unsubstituted,substituted, or substituted with R₁₀; (i) R₁₀ is selected from hydrogen,CN, substituted or unsubstituted C₁-C₆ alkyl, substituted orunsubstituted C₂-C₆ alkenyl, substituted or unsubstituted C₁-C₆ alkoxy,substituted or unsubstituted C₂-C₆ alkenyloxy, substituted orunsubstituted C₃-C₁₀ cycloalkyl, substituted or unsubstituted C₃-C₁₀cycloalkenyl, substituted or unsubstituted C₆-C₂₀ aryl, substituted orunsubstituted C₁-C₂₀ heterocyclyl, substituted or unsubstitutedS(O)_(n)C₁-C₆ alkyl, or substituted or unsubstituted N(C₁-C₆alkyl)₂R₈ issubstituted or unsubstituted C₁-C₁₂ alkenyl, substituted orunsubstituted C₁-C₁₂ alkyl, or substituted or unsubstituted C₃-C₁₀cycloalkyl, wherein each said R₁₀, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OC₁-C₆ alkyl, OC₁-C₆ haloalkyl,S(O)_(n)C₁-C₆alkyl, S(O)_(n)OC₁-C₆ alkyl, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl; (j) Q and X₁ are independently oxygen (O) or sulfur (S);(k) n is 0, 1, or 2; and (l) Z is N or C—R₃.
 2. The composition of claim1, wherein R₁, R₂, and R₄ are hydrogen.
 3. The composition of claim 1,wherein R₃ is hydrogen, F, Cl, Br, or I
 4. The composition of claim 1,wherein R₃ is hydrogen or F.
 5. The composition of claim 1, wherein R₅is selected from F, Cl, Br, I, or unsubstituted C₁-C₆ alkyl.
 6. Thecomposition of claim 1, wherein R₅ is Cl or CH₃.
 7. The composition ofclaim 1, wherein Y—C≡C—R₆ is CH₂C≡CH or CH(CH₃)C≡CH.
 8. The compositionof claim 1, wherein R₇ is (C₁-C₆)alkyl-S(O)_(n)—(C₁-C₆)alkyl,(C₁-C₆)alkyl-S(O)_(n)—(C₁-C₆)haloalkyl, or(C₁-C₆)alkyl-S(O)_(n)—(C₁-C₆)alkyl-(C₃-C₆)halocycloalkyl.
 9. Thecomposition claim 1, wherein Q and X₁ are independently oxygen (O). 10.The composition claim 1, wherein n is 0 or
 1. 11. The composition claim1, wherein Z is C—R₃.
 12. The composition of claim 1, furthercomprising: (a) one or more compounds having acaricidal, algicidal,avicidal, bactericidal, fungicidal, herbicidal, insecticidal,molluscicidal, nematicidal, rodenticidal, or virucidal properties; or(b) one or more compounds that are antifeedants, bird repellents,chemosterilants, herbicide safeners, insect attractants, insectrepellents, mammal repellents, mating disrupters, plant activators,plant growth regulators, or synergists; or (c) both (a) and (b).
 13. Thecomposition of claim 1, further comprising one or more compoundsselected from: (3-ethoxypropyl)mercury bromide, 1,2-dichloropropane,1,3-dichloropropene, 1-methylcyclopropene, 1-naphthol,2-(octylthio)ethanol, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA,2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium,2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl,2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl,2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl,2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl,2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl,2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium,2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium,2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 2iP,2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP,4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPA-sodium, 4-CPB, 4-CPP,4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate,8-phenylmercurioxyquinoline, abamectin, abscisic acid, ACC, acephate,acequinocyl, acetamiprid, acethion, acetochlor, acetophos, acetoprole,acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-methyl,acifluorfen-sodium, aclonifen, acrep, acrinathrin, acrolein,acrylonitrile, acypetacs, acypetacs-copper, acypetacs-zinc, alachlor,alanycarb, albendazole, aldicarb, aldimorph, aldoxycarb, aldrin,allethrin, allicin, allidochlor, allosamidin, alloxydim,alloxydim-sodium, allyl alcohol, allyxycarb, alorac, alpha-cypermethrin,alpha-endosulfan, ametoctradin, ametridione, ametryn, amibuzin,amicarbazone, amicarthiazol, amidithion, amidoflumet, amidosulfuron,aminocarb, aminocyclopyrachlor, aminocyclopyrachlor-methyl,aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium,aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl,amiprophos, amisulbrom, amiton, amiton oxalate, amitraz, amitrole,ammonium sulfamate, ammonium α-naphthaleneacetate, amobam, ampropylfos,anabasine, ancymidol, anilazine, anilofos, anisuron, anthraquinone,antu, apholate, aramite, arsenous oxide, asomate, aspirin, asulam,asulam-potassium, asulam-sodium, athidathion, atraton, atrazine,aureofungin, aviglycine, aviglycine hydrochloride, azaconazole,azadirachtin, azafenidin, azamethiphos, azimsulfuron, azinphos-ethyl,azinphos-methyl, aziprotryne, azithiram, azobenzene, azocyclotin,azothoate, azoxystrobin, bachmedesh, barban, barium hexafluorosilicate,barium polysulfide, barthrin, BCPC, beflubutamid, benalaxyl,benalaxyl-M, benazolin, benazolin-dimethylammonium, benazolin-ethyl,benazolin-potassium, bencarbazone, benclothiaz, bendiocarb, benfluralin,benfuracarb, benfuresate, benodanil, benomyl, benoxacor, benoxafos,benquinox, bensulfuron, bensulfuron-methyl, bensulide, bensultap,bentaluron, bentazone, bentazone-sodium, benthiavalicarb,benthiavalicarb-isopropyl, benthiazole, bentranil, benzadox,benzadox-ammonium, benzalkonium chloride, benzamacril,benzamacril-isobutyl, benzamorf, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzohydroxamic acid,benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzylbenzoate, benzyladenine, berberine, berberine chloride, beta-cyfluthrin,beta-cypermethrin, bethoxazin, bicyclopyrone, bifenazate, bifenox,bifenthrin, bifujunzhi, bilanafos, bilanafos-sodium, binapacryl,bingqingxiao, bioallethrin, bioethanomethrin, biopermethrin,bioresmethrin, biphenyl, bisazir, bismerthiazol, bispyribac,bispyribac-sodium, bistrifluron, bitertanol, bithionol, bixafen,blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid,brassinolide, brassinolide-ethyl, brevicomin, brodifacoum,brofenvalerate, brofluthrinate, bromacil, bromacil-lithium,bromacil-sodium, bromadiolone, bromethalin, bromethrin, bromfenvinfos,bromoacetamide, bromobonil, bromobutide, bromocyclen, bromo-DDT,bromofenoxim, bromophos, bromophos-ethyl, bromopropylate, bromothalonil,bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxyniloctanoate, bromoxynil-potassium, brompyrazon, bromuconazole, bronopol,bucarpolate, bufencarb, buminafos, bupirimate, buprofezin, Burgundymixture, busulfan, butacarb, butachlor, butafenacil, butamifos,butathiofos, butenachlor, butethrin, buthidazole, buthiobate, buthiuron,butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin,butroxydim, buturon, butylamine, butylate, cacodylic acid, cadusafos,cafenstrole, calcium arsenate, calcium chlorate, calcium cyanamide,calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor,captafol, captan, carbamorph, carbanolate, carbaryl, carbasulam,carbendazim, carbendazim benzenesulfonate, carbendazim sulfite,carbetamide, carbofuran, carbon disulfide, carbon tetrachloride,carbophenothion, carbosulfan, carboxazole, carboxide, carboxin,carfentrazone, carfentrazone-ethyl, carpropamid, cartap, cartaphydrochloride, carvacrol, carvone, CDEA, cellocidin, CEPC, ceralure,Cheshunt mixture, chinomethionat, chitosan, chlobenthiazone,chlomethoxyfen, chloralose, chloramben, chloramben-ammonium,chloramben-diolamine, chloramben-methyl, chloramben-methylammonium,chloramben-sodium, chloramine phosphorus, chloramphenicol,chloraniformethan, chloranil, chloranocryl, chlorantraniliprole,chlorazifop, chlorazifop-propargyl, chlorazine, chlorbenside,chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane,chlordecone, chlordimeform, chlordimeform hydrochloride,chlorempenthrin, chlorethoxyfos, chloreturon, chlorfenac,chlorfenac-ammonium, chlorfenac-sodium, chlorfenapyr, chlorfenazole,chlorfenethol, chlorfenprop, chlorfenson, chlorfensulphide,chlorfenvinphos, chlorfluazuron, chlorflurazole, chlorfluren,chlorfluren-methyl, chlorflurenol, chlorflurenol-methyl, chloridazon,chlorimuron, chlorimuron-ethyl, chlormephos, chlormequat, chlormequatchloride, chlornidine, chlornitrofen, chlorobenzilate,chlorodinitronaphthalenes, chloroform, chloromebuform, chloromethiuron,chloroneb, chlorophacinone, chlorophacinone-sodium, chloropicrin,chloropon, chloropropylate, chlorothalonil, chlorotoluron, chloroxuron,chloroxynil, chlorphonium, chlorphonium chloride, chlorphoxim,chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos,chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal,chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, chlorthiophos,chlozolinate, choline chloride, chromafenozide, cinerin I, cinerin II,cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, ciobutide,cisanilide, cismethrin, clethodim, climbazole, cliodinate, clodinafop,clodinafop-propargyl, cloethocarb, clofencet, clofencet-potassium,clofentezine, clofibric acid, clofop, clofop-isobutyl, clomazone,clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,clopyralid-olamine, clopyralid-potassium,clopyralid-tris(2-hydroxypropyl)ammonium, cloquintocet,cloquintocet-mexyl, cloransulam, cloransulam-methyl, closantel,clothianidin, clotrimazole, cloxyfonac, cloxyfonac-sodium, CMA,codlelure, colophonate, copper acetate, copper acetoarsenite, copperarsenate, copper carbonate, basic, copper hydroxide, copper naphthenate,copper oleate, copper oxychloride, copper silicate, copper sulfate,copper zinc chromate, coumachlor, coumafuryl, coumaphos, coumatetralyl,coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol,crimidine, crotamiton, crotoxyphos, crufomate, cryolite, cue-lure,cufraneb, cumyluron, cuprobam, cuprous oxide, curcumenol, cyanamide,cyanatryn, cyanazine, cyanofenphos, cyanophos, cyanthoate,cyantraniliprole, cyazofamid, cybutryne, cyclafuramid, cyclanilide,cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin,cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid,cyflumetofen, cyfluthrin, cyhalofop, cyhalofop-butyl, cyhalothrin,cyhexatin, cymiazole, cymiazole hydrochloride, cymoxanil, cyometrinil,cypendazole, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin,cyprazine, cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid,cyprosulfamide, cyromazine, cythioate, daimuron, dalapon,dalapon-calcium, dalapon-magnesium, dalapon-sodium, daminozide,dayoutong, dazomet, dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT,debacarb, decafentin, decarbofuran, dehydroacetic acid, delachlor,deltamethrin, demephion, demephion-O, demephion-S, demeton,demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, desmedipham, desmetryn,d-fanshiluquebingjuzhi, diafenthiuron, dialifos, di-allate, diamidafos,diatomaceous earth, diazinon, dibutyl phthalate, dibutyl succinate,dicamba, dicamba-diglycolamine, dicamba-dimethylammonium,dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl,dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-trolamine,dicapthon, dichlobenil, dichlofenthion, dichlofluanid, dichlone,dichloralurea, dichlorbenzuron, dichlorflurenol, dichlorflurenol-methyl,dichlormate, dichlormid, dichlorophen, dichlorprop,dichlorprop-2-ethylhexyl, dichlorprop-butotyl,dichlorprop-dimethylammonium, dichlorprop-ethylammonium,dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,dichlorprop-P-2-ethylhexyl, dichlorprop-P-dimethylammonium,dichlorprop-potassium, dichlorprop-sodium, dichlorvos, dichlozoline,diclobutrazol, diclocymet, diclofop, diclofop-methyl, diclomezine,diclomezine-sodium, dicloran, diclosulam, dicofol, dicoumarol, dicresyl,dicrotophos, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat,diethamquat dichloride, diethatyl, diethatyl-ethyl, diethofencarb,dietholate, diethyl pyrocarbonate, diethyltoluamide, difenacoum,difenoconazole, difenopenten, difenopenten-ethyl, difenoxuron,difenzoquat, difenzoquat metilsulfate, difethialone, diflovidazin,diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr-sodium,diflumetorim, dikegulac, dikegulac-sodium, dilor, dimatif, dimefluthrin,dimefox, dimefuron, dimepiperate, dimetachlone, dimetan, dimethacarb,dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin,dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate,dimethyl phthalate, dimethylvinphos, dimetilan, dimexano, dimidazon,dimoxystrobin, dinex, dinex-diclexine, dingjunezuo, diniconazole,diniconazole-M, dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinosebacetate, dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium,dinoseb-trolamine, dinosulfon, dinotefuran, dinoterb, dinoterb acetate,dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion,diphacinone, diphacinone-sodium, diphenamid, diphenyl sulfone,diphenylamine, dipropalin, dipropetryn, dipyrithione, diquat, diquatdibromide, disparlure, disul, disulfiram, disulfoton, disul-sodium,ditalimfos, dithianon, dithicrofos, dithioether, dithiopyr, diuron,d-limonene, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicinhydrochloride, dodicin-sodium, dodine, dofenapyn, dominicalure,doramectin, drazoxolon, DSMA, dufulin, EBEP, EBP, ecdysterone,edifenphos, eglinazine, eglinazine-ethyl, emamectin, emamectin benzoate,EMPC, empenthrin, endosulfan, endothal, endothal-diammonium,endothal-dipotassium, endothal-disodium, endothion, endrin,enestroburin, EPN, epocholeone, epofenonane, epoxiconazole,eprinomectin, epronaz, EPTC, erbon, ergocalciferol, erlujixiancaoan,esdepallethrine, esfenvalerate, esprocarb, etacelasil, etaconazole,etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron,ethametsulfuron-methyl, ethaprochlor, ethephon, ethidimuron,ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol,ethoate-methyl, ethofumesate, ethohexadiol, ethoprophos, ethoxyfen,ethoxyfen-ethyl, ethoxyquin, ethoxysulfuron, ethychlozate, ethylformate, ethyl α-naphthaleneacetate, ethyl-DDD, ethylene, ethylenedibromide, ethylene dichloride, ethylene oxide, ethylicin, ethylmercury2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercurybromide, ethylmercury chloride, ethylmercury phosphate, etinofen,etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos,eugenol, EXD, famoxadone, famphur, fenamidone, fenaminosulf, fenamiphos,fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole,fenbutatin oxide, fenchlorazole, fenchlorazole-ethyl, fenchlorphos,fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitropan,fenitrothion, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypropyl,fenoprop-butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl,fenoprop-methyl, fenoprop-potassium, fenothiocarb, fenoxacrim,fenoxanil, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P,fenoxaprop-P-ethyl, fenoxasulfone, fenoxycarb, fenpiclonil,fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine,fenpyroximate, fenridazon, fenridazon-potassium, fenridazon-propyl,fenson, fensulfothion, fenteracol, fenthiaprop, fenthiaprop-ethyl,fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride,fentin hydroxide, fentrazamide, fentrifanil, fenuron, fenuron TCA,fenvalerate, ferbam, ferimzone, ferrous sulfate, fipronil, flamprop,flamprop-isopropyl, flamprop-M, flamprop-methyl, flamprop-M-isopropyl,flamprop-M-methyl, flazasulfuron, flocoumafen, flometoquin, flonicamid,florasulam, fluacrypyrim, fluazifop, fluazifop-butyl, fluazifop-methyl,fluazifop-P, fluazifop-P-butyl, fluazinam, fluazolate, fluazuron,flubendiamide, flubenzimine, flucarbazone, flucarbazone-sodium,flucetosulfuron, fluchloralin, flucofuron, flucycloxuron, flucythrinate,fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerim,flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr-ethyl,flufiprole, flumethrin, flumetover, flumetralin, flumetsulam, flumezin,flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, flumorph,fluometuron, fluopicolide, fluopyram, fluorbenside, fluoridamid,fluoroacetamide, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl,fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluotrimazole,fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate,flupropanate-sodium, flupyradifurone, flupyrsulfuron,flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluquinconazole,flurazole, flurenol, flurenol-butyl, flurenol-methyl, fluridone,flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl,flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide,fluthiacet, fluthiacet-methyl, flutianil, flutolanil, flutriafol,fluvalinate, fluxapyroxad, fluxofenim, folpet, fomesafen,fomesafen-sodium, fonofos, foramsulfuron, forchlorfenuron, formaldehyde,formetanate, formetanate hydrochloride, formothion, formparanate,formparanate hydrochloride, fosamine, fosamine-ammonium, fosetyl,fosetyl-aluminium, fosmethilan, fospirate, fosthiazate, fosthietan,frontalis, fuberidazole, fucaojing, fucaomi, funaihecaoling,fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr,furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin,furfural, furilazole, furmecyclox, furophanate, furyloxyfen,gamma-cyhalothrin, gamma-HCH, genii, gibberellic acid, gibberellins,gliftor, glufosinate, glufosinate-ammonium, glufosinate-P,glufosinate-P-ammonium, glufosinate-P-sodium, glyodin, glyoxime,glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium,glyphosate-isopropylammonium, glyphosate-monoammonium,glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium,glyphosine, gossyplure, grandlure, griseofulvin, guazatine, guazatineacetates, halacrinate, halfenprox, halofenozide, halosafen,halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop,haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl,haloxyfop-P-methyl, haloxyfop-sodium, HCH, hemel, hempa, HEOD,heptachlor, heptenophos, heptopargil, heterophos, hexachloroacetone,hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole,hexaflumuron, hexaflurate, hexalure, hexamide, hexazinone, hexylthiofos,hexythiazox, HHDN, holosulf, huancaiwo, huangcaoling, huanjunzuo,hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanide,hydroprene, hymexazol, hyquincarb, IAA, IBA, icaridin, imazalil,imazalil nitrate, imazalil sulfate, imazamethabenz,imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic,imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin,imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr,imazethapyr-ammonium, imazosulfuron, imibenconazole, imicyafos,imidacloprid, imidaclothiz, iminoctadine, iminoctadine triacetate,iminoctadine trialbesilate, imiprothrin, inabenfide, indanofan,indaziflam, indoxacarb, inezin, iodobonil, iodocarb, iodomethane,iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium,iofensulfuron, iofensulfuron-sodium, ioxynil, ioxynil octanoate,ioxynil-lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarbazone,iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol,IPSP, isamidofos, isazofos, isobenzan, isocarbamid, isocarbophos,isocil, isodrin, isofenphos, isofenphos-methyl, isolan, isomethiozin,isonoruron, isopolinate, isoprocarb, isopropalin, isoprothiolane,isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron,isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen-ethyl,isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izopamfos,japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid,jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan,jiecaoxi, jodfenphos, juvenile hormone I, juvenile hormone II, juvenilehormone III, kadethrin, karbutilate, karetazan, karetazan-potassium,kasugamycin, kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox,ketospiradox-potassium, kinetin, kinoprene, kresoxim-methyl, kuicaoxi,lactofen, lambda-cyhalothrin, latilure, lead arsenate, lenacil,lepimectin, leptophos, lindane, lineatin, linuron, lirimfos, litlure,looplure, lufenuron, lvdingjunzhi, lvxiancaolin, lythidathion, MAA,malathion, maleic hydrazide, malonoben, maltodextrin, MAMA, mancopper,mancozeb, mandipropamid, maneb, matrine, mazidox, MCPA,MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium,MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl,MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl,MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mebenil,mecarbam, mecarbinzid, mecarphon, mecoprop, mecoprop-2-ethylhexyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-2-ethylhexyl,mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium,mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medimeform,medinoterb, medinoterb acetate, medlure, mefenacet, mefenpyr,mefenpyr-diethyl, mefluidide, mefluidide-diolamine,mefluidide-potassium, megatomoic acid, menazon, mepanipyrim,meperfluthrin, mephenate, mephosfolan, mepiquat, mepiquat chloride,mepiquat pentaborate, mepronil, meptyldinocap, mercuric chloride,mercuric oxide, mercurous chloride, merphos, mesoprazine, mesosulfuron,mesosulfuron-methyl, mesotrione, mesulfen, mesulfenfos, metaflumizone,metalaxyl, metalaxyl-M, metaldehyde, metam, metam-ammonium, metamifop,metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron,metazoxolon, metconazole, metepa, metflurazon, methabenzthiazuron,methacrifos, methalpropalin, methamidophos, methasulfocarb, methazole,methfuroxam, methidathion, methiobencarb, methiocarb,methiopyrisulfuron, methiotepa, methiozolin, methiuron, methocrotophos,methometon, methomyl, methoprene, methoprotryne, methoquin-butyl,methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methylapholate, methyl bromide, methyl eugenol, methyl iodide, methylisothiocyanate, methylacetophos, methylchloroform, methyldymron,methylene chloride, methylmercury benzoate, methylmercury dicyandiamide,methylmercury pentachlorophenoxide, methylneodecanamide, metiram,metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb,metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone,metribuzin, metsulfovax, metsulfuron, metsulfuron-methyl, mevinphos,mexacarbate, mieshuan, milbemectin, milbemycin oxime, milneb, mipafox,mirex, MNAF, moguchun, molinate, molosultap, monalide, monisouron,monochloroacetic acid, monocrotophos, monolinuron, monosulfuron,monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquatdichloride, moroxydine, moroxydine hydrochloride, morphothion, morzid,moxidectin, MSMA, muscalure, myclobutanil, myclozolin,N-(ethylmercury)-p-toluenesulphonanilide, nabam, naftalofos, naled,naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthoxyaceticacids, naproanilide, napropamide, naptalam, naptalam-sodium, natamycin,neburon, niclosamide, niclosamide-olamine, nicosulfuron, nicotine,nifluridide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin,nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl,norbormide, norflurazon, nornicotine, noruron, novaluron, noviflumuron,nuarimol, OCH, octachlorodipropyl ether, octhilinone, ofurace,omethoate, orbencarb, orfralure, ortho-dichlorobenzene, orthosulfamuron,oryctalure, orysastrobin, oryzalin, osthol, ostramone, oxabetrinil,oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon,oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone,oxine-copper, oxolinic acid, oxpoconazole, oxpoconazole fumarate,oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyfluorfen,oxymatrine, oxytetracycline, oxytetracycline hydrochloride,paclobutrazol, paichongding, para-dichlorobenzene, parafluron, paraquat,paraquat dichloride, paraquat dimetilsulfate, parathion,parathion-methyl, parinol, pebulate, pefurazoate, pelargonic acid,penconazole, pencycuron, pendimethalin, penflufen, penfluron,penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad, pentmethrin,pentoxazone, perfluidone, permethrin, pethoxamid, phenamacril, phenazineoxide, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl,phenobenzuron, phenothrin, phenproxide, phenthoate, phenylmercuriurea,phenylmercury acetate, phenylmercury chloride, phenylmercury derivativeof pyrocatechol, phenylmercury nitrate, phenylmercury salicylate,phorate, phosacetim, phosalone, phosdiphen, phosfolan, phosfolan-methyl,phosglycin, phosmet, phosnichlor, phosphamidon, phosphine, phosphocarb,phosphorus, phostin, phoxim, phoxim-methyl, phthalide, picloram,picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl,picloram-olamine, picloram-potassium, picloram-triethylammonium,picloram-tris(2-hydroxypropyl)ammonium, picolinafen, picoxystrobin,pindone, pindone-sodium, pinoxaden, piperalin, piperonyl butoxide,piperonyl cyclonene, piperophos, piproctanyl, piproctanyl bromide,piprotal, pirimetaphos, pirimicarb, pirimioxyphos, pirimiphos-ethyl,pirimiphos-methyl, plifenate, polycarbamate, polyoxins, polyoxorim,polyoxorim-zinc, polythialan, potassium arsenite, potassium azide,potassium cyanate, potassium gibberellate, potassium naphthenate,potassium polysulfide, potassium thiocyanate, potassiumα-naphthaleneacetate, pp′-DDT, prallethrin, precocene I, precocene II,precocene III, pretilachlor, primidophos, primisulfuron,primisulfuron-methyl, probenazole, prochloraz, prochloraz-manganese,proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol,profluralin, profluthrin, profoxydim, proglinazine, proglinazine-ethyl,prohexadione, prohexadione-calcium, prohydrojasmon, promacyl, promecarb,prometon, prometryn, promurit, propachlor, propamidine, propamidinedihydrochloride, propamocarb, propamocarb hydrochloride, propanil,propaphos, propaquizafop, propargite, proparthrin, propazine,propetamphos, propham, propiconazole, propineb, propisochlor, propoxur,propoxycarbazone, propoxycarbazone-sodium, propyl isome,propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin,prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothiocarbhydrochloride, prothioconazole, prothiofos, prothoate, protrifenbute,proxan, proxan-sodium, prynachlor, pydanon, pymetrozine, pyracarbolid,pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyraflufen-ethyl,pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotole,pyrazolynate, pyrazophos, pyrazosulfuron, pyrazosulfuron-ethyl,pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II,pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl, pyribencarb,pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol, pyridalyl,pyridaphenthion, pyridate, pyridinitril, pyrifenox, pyrifluquinazon,pyriftalid, pyrimethanil, pyrimidifen, pyriminobac, pyriminobac-methyl,pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole,pyripropanol, pyriproxyfen, pyrithiobac, pyrithiobac-sodium, pyrolan,pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur, quassia,quinacetol, quinacetol sulfate, quinalphos, quinalphos-methyl,quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine,quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop,quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl,quizalofop-P-tefuryl, quwenzhi, quyingding, rabenzazole, rafoxanide,rebemide, resmethrin, rhodethanil, rhodojaponin-III, ribavirin,rimsulfuron, rotenone, ryania, saflufenacil, saijunmao, saisentong,salicylanilide, sanguinarine, santonin, schradan, scilliroside,sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz,semiamitraz chloride, sesamex, sesamolin, sethoxydim, shuangjiaancaolin,siduron, siglure, silafluofen, silatrane, silica gel, silthiofam,simazine, simeconazole, simeton, simetryn, sintofen, SMA, S-metolachlor,sodium arsenite, sodium azide, sodium chlorate, sodium fluoride, sodiumfluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodiumorthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide,sodium thiocyanate, sodium α-naphthaleneacetate, sophamide, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine,streptomycin, streptomycin sesquisulfate, strychnine, sulcatol,sulcofuron, sulcofuron-sodium, sulcotrione, sulfallate, sulfentrazone,sulfiram, sulfluramid, sulfometuron, sulfometuron-methyl, sulfosulfuron,sulfotep, sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid,sulfuryl fluoride, sulglycapin, sulprofos, sultropen, swep,tau-fluvalinate, tavron, tazimcarb, TCA, TCA-ammonium, TCA-calcium,TCA-ethadyl, TCA-magnesium, TCA-sodium, TDE, tebuconazole, tebufenozide,tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron,tecloftalam, tecnazene, tecoram, teflubenzuron, tefluthrin,tefuryltrione, tembotrione, temephos, tepa, TEPP, tepraloxydim,terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton,terbuthylazine, terbutryn, tetcyclacis, tetrachloroethane,tetrachlorvinphos, tetraconazole, tetradifon, tetrafluron, tetramethrin,tetramethylfluthrin, tetramine, tetranactin, tetrasul, thallium sulfate,thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid,thiadifluor, thiamethoxam, thiapronil, thiazafluron, thiazopyr,thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone,thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, thiocyclam,thiocyclam hydrochloride, thiocyclam oxalate, thiodiazole-copper,thiodicarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon,thionazin, thiophanate, thiophanate-methyl, thioquinox,thiosemicarbazide, thiosultap, thiosultap-diammonium,thiosultap-disodium, thiosultap-monosodium, thiotepa, thiram,thuringiensin, tiadinil, tiaojiean, tiocarbazil, tioclorim, tioxymid,tirpate, tolclofos-methyl, tolfenpyrad, tolylfluanid, tolylmercuryacetate, topramezone, tralkoxydim, tralocythrin, tralomethrin,tralopyril, transfluthrin, transpermethrin, tretamine, triacontanol,triadimefon, triadimenol, triafamone, tri-allate, triamiphos,triapenthenol, triarathene, triarimol, triasulfuron, triazamate,triazbutil, triaziflam, triazophos, triazoxide, tribenuron,tribenuron-methyl, tribufos, tributyltin oxide, tricamba, trichlamide,trichlorfon, trichlormetaphos-3, trichloronat, triclopyr,triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium,tricyclazole, tridemorph, tridiphane, trietazine, trifenmorph,trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium,triflumizole, triflumuron, trifluralin, triflusulfuron,triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, triforine,trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac,trinexapac-ethyl, triprene, tripropindan, triptolide, tritac,triticonazole, tritosulfuron, trunc-call, uniconazole, uniconazole-P,urbacide, uredepa, valerate, validamycin, valifenalate, valone,vamidothion, vangard, vaniliprole, vernolate, vinclozolin, warfarin,warfarin-potassium, warfarin-sodium, xiaochongliulin, xinjunan,xiwojunan, XMC, xylachlor, xylenols, xylylcarb, yishijing, zarilamid,zeatin, zengxiaoan, zeta-cypermethrin, zinc naphthenate, zinc phosphide,zinc thiazole, zineb, ziram, zolaprofos, zoxamide, zuomihuanglong,α-chlorohydrin, α-ecdysone, α-multistriatin, and α-naphthaleneaceticacid
 14. The composition of claim 1, further comprising anagriculturally acceptable carrier.
 15. The composition of claim 1,wherein the compound is in the form of a pesticidally acceptable acidaddition salt, a salt derivative, or a hydrate.
 16. The composition ofclaim 1, wherein the compound is a resolved stereoisomer.
 17. Thecomposition of claim 1, wherein the compound is in the form a crystalpolymorph.
 18. The composition of claim 1, wherein the compoundcomprises a ²H in place of ¹H, or ¹³C in place of a ¹²C, or both. 19.The composition of claim 1, further comprising a biopesticide.
 20. Thecomposition of claim 1, further comprising at least one of the followingcompounds: (a)3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;(b)3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;(c) 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone; (d)4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone; (e)3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;(f) 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide; (g)2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; (h)2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide; (i)2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide; (j)2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide; (k)2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide; (l)2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfonamide; (m)3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;(n)N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone; (o)N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazonenicotine; (p)O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-methylthiocarbonate; (q)(E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;(r)1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;(s) 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate;and (t)N-Ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazine.21. The composition of claim 1, further comprising a compound having oneor more of the following modes of action: acetylcholinesteraseinhibitor; sodium channel modulator; chitin biosynthesis inhibitor; GABAand glutamate-gated chloride channel antagonist; GABA andglutamate-gated chloride channel agonist; acetylcholine receptoragonist; acetylcholine receptor antagonist; MET I inhibitor;Mg-stimulated ATPase inhibitor; nicotinic acetylcholine receptor; Midgutmembrane disrupter; oxidative phosphorylation disrupter, and ryanodinereceptor (RyRs).
 22. The composition of claim 1, further comprising aseed.
 23. The composition of claim 1, further comprising a seed that hasbeen genetically modified to express one or more specialized traits. 24.The composition of to claim 1, wherein the composition is encapsulatedinside, or placed on the surface of, a capsule.
 25. The composition ofclaim 1, wherein the composition is encapsulated inside, or placed onthe surface of, a capsule, wherein the capsule has a diameter of about100 microns to about 900 nanometers, or about 10 microns to about 900microns.
 26. The composition of claim 1, further comprising ammoniumsulfate.
 27. A method of controlling pest, comprising applying thecomposition of claim 26, to an area to control a pest, in an amountsufficient to control such pest.
 28. A process comprising applying thecomposition of claim 1, to an area to control a pest, in an amountsufficient to control such pest.
 29. The process of claim 28, whereinthe pest is selected from beetles, earwigs, cockroaches, flies. aphids,scales, whiteflies, leafhoppers, ants, wasps, termites, moths,butterflies, lice, grasshoppers, locusts, crickets, fleas, thrips,bristletails, mites, ticks, nematodes, and symphylans.
 30. The processof claim 28, wherein the pest is from the Phyla Nematoda or Arthropoda.31. The process of claim 28, wherein the pest is from the SubphylaChelicerata, Myriapoda, or Hexapoda.
 32. The process of claim 28,wherein the pest is from the Class of Arachnida, Symphyla, or Insecta.33. The process of claim 28, wherein the pest is from the OrderAnoplura, Order Coleoptera, Order Dermaptera, Order Blattaria, OrderDiptera, Order Hemiptera, Order Hymenoptera, Order Isoptera, OrderLepidoptera, Order Mallophaga, Order Orthoptera, Order Siphonaptera,Order Thysanoptera, Order Thysanura, Order Acarina, or Order Symphyla.34. The process of claim 28, wherein the pest is MYZUPE or BEMITA. 35.The process of claim 28, comprising applying the composition from about0.01 grams per hectare to about 5000 grams per hectare.
 36. The processof claim 28, comprising applying the composition from about 0.1 gramsper hectare to about 500 grams per hectare.
 37. The process of claim 28,comprising applying the composition from about 1 gram per hectare toabout 50 grams per hectare.
 38. The process of claim 28, wherein thearea to control a pest is an area where apples, corn, cotton, soybeans,canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa,lettuce, strawberries, tomatoes, peppers, crucifers, pears, tobacco,almonds, sugar beets, or beans, are growing, or the seeds thereof aregoing to be planted.
 39. A process comprising applying the compositionof claim 1 to a genetically modified plant that has been geneticallymodified to express one or more specialized traits.
 40. A method ofpreparing the composition of claim 1, the method comprising:

reacting a tert-butoxy carbamate compound of formula 1-1 with a base andthen with an electrophile of formula 1-2, wherein LG is halogen, alkylsulfonate, or aryl sulfonate, to afford a thiazole compound of formula1-3; treating the thiazole compound of formula 1-3 with an acid toafford a corresponding salt of formula 1-4; and reacting the salt offormula 1-4 with an acid chloride (X=Cl) or a carboxylic acid (X=OH) offormula 1-5, to provide the compound of formula I, wherein R₁, R₂, R₄,R₅, R₆, R₇, Y, and Z are defined as in claim
 41. A method of preparingthe composition of claim 1, the method comprising: reacting atert-butoxy carbamate compound of formula 2-1 with a base and then withan electrophile of formula 2-2, to afford a compound of formula 2-3;treating the compound of formula 2-3 with an acid to afford acorresponding salt of the formula 2-4; and reacting the salt of formula2-4 with an acid chloride of the formula 2-5, where n′=1 or 2, toprovide a compound of the formula 2-6, wherein R₅, R₆, n′, and Z, aredefined as in claim
 1.


42. A method of controlling pests, comprising applying the pesticidalcomposition of claim 1 near a population of pests.
 43. The method ofclaim 42, wherein the pesticidal composition further comprises aphytologically-acceptable inert carrier.
 44. The method of claim 42,wherein the pesticidal composition further comprises an additiveselected from the group consisting of a surfactant, a stabilizer, anemetic agent, a disintegrating agent, an antifoaming agent, a wettingagent, a dispersing agent, a binding agent, dye, and filler.